Self-powered water-vapor battery dressing with functions of autonomous water release and water supplement and application

Abstract

The present application relates to the field of biomedical engineering, specifically provides a kind of self-powered water-volt battery dressing with self-release water and water function, the dressing innovationally integrates temperature-sensitive conductive hydrogel layer and water-volt power generation layer, realizes the self-adaptive, self-sustaining intervention to wound microenvironment, through the unique "water storage-release-water" closed-loop mechanism, system utilizes body temperature trigger water release on demand, and realizes the self-supply of fuel and energy recycling by absorbing tissue exudate and external water environment moisture, so as to overcome the technical bottleneck that the energy source of existing self-powered system is unstable, intermittent supply, ensure that continuous, stable therapeutic electric stimulation is provided in the whole healing period;Compared with traditional treatment methods, the dressing can significantly accelerate wound closure and promote ordered and high-quality regeneration repair.

Description

Technical Field

[0001] This invention relates to the field of biomedical engineering, specifically to a self-powered hydrovoltaic battery dressing with both autonomous water release and water replenishment functions, and its application. Background Technology

[0002] High-quality skin injury repair is a common challenge in clinical medicine. Whether it is an acute wound caused by trauma or surgical incision, or a difficult-to-heal wound such as diabetic foot ulcers, venous ulcers, or large-area burns, how to shorten healing time and reduce scar formation while ensuring repair quality has always been a key issue that needs to be addressed in clinical practice.

[0003] The mechanism of action of the endogenous bioelectric field, as an important physical signal guiding directional cell migration and promoting orderly tissue regeneration, has been widely confirmed. Under physiological conditions, a transepithelial potential exists between the epithelial layer and the dermis of the skin. When the integrity of the skin is disrupted, a potential difference is formed between the damaged area and the surrounding intact tissue, generating an endogenous injury current. This creates a steady-state electric field with an intensity of approximately 40–200 mV / mm, directed towards the center of the wound. This endogenous electric field is considered one of the earliest repair signals generated after tissue injury, providing directional guidance for cell migration and serving as a key regulatory factor for orderly tissue regeneration.

[0004] Based on the above research, exogenous electrical stimulation, as an effective adjunct to physical therapy, has shown significant potential in promoting the healing of chronic wounds, burns, and other refractory wounds. Existing research indicates that its mechanism of action encompasses several key aspects, including promoting epithelial cell migration, enhancing fibroblast activity, stimulating angiogenesis, and regulating local inflammatory responses. Although electrical stimulation has a clear efficacy in promoting wound healing, traditional electrical stimulation therapy has significant limitations in clinical application. Traditional electrical stimulation therapy typically relies on bulky external power supplies and rigid electrodes, resulting in limited patient mobility, fixed treatment settings, poor comfort, and high levels of professional expertise required for operation, severely restricting its widespread application in home and daily rehabilitation settings. Therefore, developing an electrical stimulation device that can be independent of external power sources, is portable, and wearable has become a pressing technical problem for those skilled in the art.

[0005] To reduce reliance on external power sources, researchers have explored various self-powered systems based on energy harvesting principles. For example, invention patent CN113893015A discloses a wearable dressing based on a triboelectric nanogenerator that can generate pulsed currents using human movement. However, its electrical output is unstable and discontinuous, highly dependent on uncontrollable intermittent physical activity, and cannot provide continuous treatment when the patient is at rest. While enzyme biofuel cells can generate electricity using glucose in tissue fluid, converting chemical energy into electrical energy, their core enzymes are easily inactivated in the complex and dynamic wound microenvironment, posing significant challenges to long-term stability and reliability. Although the aforementioned systems have made progress in "self-powered" technology, their power generation behavior is often limited by the intermittency of external stimuli or the biological stability of the materials themselves, making it difficult to achieve continuous and controllable electrical signal output. In addition, hydrogels, due to their high water content, excellent biocompatibility, and tunable physicochemical properties, have become ideal novel dressing substrates. For example, invention patent CN110483808A discloses a thermosensitive hydrogel that can reversibly swell and contract in response to changes in body temperature, used for intelligent drug release, and exhibiting good ability to maintain a moist environment. However, such materials are essentially still functionally passive, only able to respond to external stimuli, and do not have the ability to actively generate therapeutic bioelectric signals.

[0006] In recent years, the water-voltaic effect has attracted widespread attention as an emerging energy conversion mechanism. Existing studies have reported that carbon nanomaterials can generate electricity through water evaporation, providing a new approach to extracting electrical energy from environmental moisture. However, existing water-voltaic power generation devices typically rely on a continuous external water supply to maintain output. In skin wound applications, it is difficult for devices to obtain a stable external water source. While wound exudate can serve as a local moisture source, its total amount is limited, its duration is short, and it gradually decreases as the wound heals. Therefore, it is difficult to meet the requirements for electrical stimulation intensity and duration during wound treatment.

[0007] In summary, the current technological landscape is clearly fragmented: self-powered systems (such as triboelectric, enzyme fuel cells, and basic hydrovoltaic devices) often lack the stable moist environment maintenance capability and biocompatibility necessary for excellent wound dressings, and their energy sources are unreliable; while materials with excellent dressing properties (such as hydrogels) generally lack self-generating capabilities, making active electrical stimulation therapy impossible. Therefore, a long-standing unresolved technical challenge in this field remains: how to construct an integrated wound treatment system that deeply integrates intelligent moisture management, long-lasting self-powered operation, and active electrical stimulation therapy, thereby achieving adaptive and self-sustaining intelligent intervention of the dynamic wound microenvironment. Summary of the Invention

[0008] The primary objective of this invention is to provide a self-powered hydrovoltaic battery dressing that combines self-release and self-replenishment of water. The self-powered hydrovoltaic battery dressing includes a hydrophilic layer and a hydrophobic layer disposed on both sides of a square filter paper. A cathode and an anode are disposed at opposite ends of the hydrophilic layer. A temperature-sensitive conductive hydrogel is covered between the cathode and the anode. The dressing is then encapsulated with a thin film, with windows opened on both sides of the film. The thermosensitive conductive hydrogel is obtained by adding PEDOT / PSS aqueous dispersion to a mixed solution of sodium alginate, N-isopropylacrylamide, N,N-methylenebisacrylamide, acrylamide phenylboronic acid and photoinitiator, followed by photocrosslinking and then chemical crosslinking.

[0009] Preferably, the addition ratios of sodium alginate, N-isopropylacrylamide, N,N-methylenebisacrylamide, acrylamide-phenylboronic acid, and photoinitiator are 2:20:0.1:0.1:0.4, respectively.

[0010] Preferably, the addition ratio of the PEDOT / PSS aqueous dispersion is 0.02-0.08:100.

[0011] Preferably, the hydrophilic layer is obtained by coating the filter paper surface with a carbon black ethanol dispersion, and the hydrophobic layer is obtained by coating the filter paper surface with paraffin wax.

[0012] Preferably, the film is a polyethylene terephthalate film.

[0013] Preferably, the temperature-sensitive conductive hydrogel is prepared by the following method: (1) Sodium alginate, N-isopropylacrylamide, N,N-methylenebisacrylamide, acrylamide phenylboronic acid and photoinitiator 2959 were dissolved in deionized water and stirred at room temperature until they were uniform and transparent. High-purity nitrogen was introduced to remove dissolved oxygen to obtain sodium alginate / N-isopropylacrylamide sol. (2) Take the sodium alginate / N-isopropylacrylamide sol obtained in step (1), add PEDOT / PSS aqueous dispersion to it, shake until it is mixed evenly, and obtain sodium alginate / N-isopropylacrylamide / PEDOT / PSS sol; (3) Pour the sodium alginate / N-isopropylacrylamide / PEDOT / PSS sol obtained in step (2) into a polytetrafluoroethylene mold, control the temperature in an ice water bath, and irradiate with ultraviolet light to form a nascent hydrogel network. (4) Remove the nascent hydrogel network obtained in step (3) from the mold and immerse it in CaCl2 solution for 5-30 min; (5) Place the hydrogel obtained in step (4) in deionized water and soak and wash it to obtain a temperature-sensitive conductive hydrogel.

[0014] Preferably, the center wavelength of the ultraviolet light in step (3) is 365 nm and the light intensity is 10 mW / cm. 2 .

[0015] Preferably, the concentration of the CaCl2 solution in step (4) is 1 wt%.

[0016] A second object of the present invention is to provide the use of the self-powered hydrovoltaic battery dressing in the preparation of products for the prevention and / or treatment of indications related to skin damage.

[0017] A third objective of the present invention is to provide a dressing for repairing skin damage, comprising, or prepared from, the self-powered hydrovoltaic battery dressing described above.

[0018] The beneficial effects of this invention are: This invention provides a self-powered hydrovoltaic battery dressing that combines autonomous water release and water replenishment functions, and has the following advantages: (1) System Integration and Functional Restructuring: This invention breaks through the paradigm of simple functional superposition. Through the deep coupling of material design and system architecture, it realizes the synergy and reconstruction of functional units. The temperature-sensitive conductive hydrogel layer transforms from a traditional passive water storage carrier into an active response unit integrating "intelligent hydraulic engine", "dynamic electrolyte reservoir" and "conductive dressing", which together with the hydrovoltaic power generation layer constitutes an intelligent system for energy supply, wound treatment and self-maintenance. Without relying on external power source, patient movement, or intermittent energy supply, it can achieve continuous and stable power output by relying solely on the water storage and release of the hydrogel. This is fundamentally different from self-powered methods that rely on external mechanical energy, light energy or specific biochemical reactions, and also different from traditional dressings that lack active regulation capabilities.

[0019] (2) Overcoming the problem of long-term stable power supply: This invention creatively constructs an energy management mechanism of "water storage - trigger release - continuous replenishment". The temperature-sensitive conductive hydrogel can store water in advance and release it on demand under the action of body temperature, ensuring that the dressing can start generating electricity quickly after being attached to the wound. At the same time, it can absorb wound exudate to replenish water in situ, and can also absorb and store water in the external water environment to maintain the continuous supply of power generation medium. It effectively overcomes the problem of traditional water-voltaic devices relying on a single external water supply and insufficient output continuity, and realizes long-term stable power supply suitable for the dynamic healing process of wounds.

[0020] (3) Achieving intelligent and coordinated treatment: The electrical stimulation signal generated by this invention is naturally coupled with the physiological state (temperature, exudation) and healing process of the wound, demonstrating intelligent and temporal biological regulation capabilities. Animal experimental results show that compared with commercial 3M dressings, this invention can significantly accelerate the healing process, increasing the wound closure rate of a rat full-thickness skin defect model from approximately 85.0% to over 98.4% on day 14. More importantly, it can dynamically regulate key healing factors: in the late inflammation / early proliferation phase (e.g., day 7), it significantly upregulates factors related to epidermal regeneration and angiogenesis (e.g., EGF, CD31); in the remodeling phase (e.g., day 14), it appropriately downregulates factors related to excessive fibrosis and scar formation (e.g., TGF-β, α-SMA). It generates electrical signals that match the characteristics of the endogenous bioelectric field and can effectively regulate cell behavior. This dynamic electrical stimulation regulation, synchronized with the physiological healing rhythm, is the core advantage for achieving high-quality, low-scarring healing, which is difficult to achieve with external electrical stimulation with fixed parameters or other self-powered systems with uncontrollable output. Attached Figure Description

[0021] The present invention will now be described in further detail with reference to the accompanying drawings.

[0022] Figure 1 This is a flowchart illustrating the preparation process of the hydrovoltaic battery dressing of the present invention. Note: This includes the preparation of hydrovoltaic power generation electrodes, the preparation of temperature-sensitive conductive hydrogels, and the assembly of hydrovoltaic battery dressings.

[0023] Figure 2 The output current curves of the hydrovoltaic battery dressing of the present invention in vitro and in living wounds are shown. Note: Output current curves of (AC) SPP200A, SPP400A, and SPP800A hydroelectric battery dressings in vitro and (D) SPP800A hydroelectric battery dressing at a live wound site.

[0024] Figure 3 This is a photograph of a physical demonstration of the invention, showing how a series-connected battery pack drives an LED light and a calculator.

[0025] Figure 4 This invention relates to the electrochemical performance, microstructure, and water absorption rate changes of the hydrovoltaic battery dressing. Note: (A) Resistance changes of SPP200A, SPP400A, and SPP800A hydrovoltaic battery dressings during multiple dehydration-rehydration cycles; (BC) SEM images of SPP800A temperature-sensitive conductive hydrogel and hydrovoltaic power generation layer (porous carbon film); (D) Electrochemical impedance spectroscopy of SPP200A, SPP400A, and SPP800A hydrovoltaic battery dressings; (E) Water absorption rate changes of SPP200A, SPP400A, and SPP800A hydrovoltaic battery dressings during multiple dehydration-rehydration cycles.

[0026] Figure 5 Characterization of the physicochemical properties of the thermosensitive conductive hydrogel used in the water-voltaic battery dressing of the present invention. Note: (A) FTIR of SPP800A thermosensitive conductive hydrogel; (B) Initial water content of SPP200A, SPP400A, and SPP800A thermosensitive conductive hydrogels; (C) Swelling kinetics curves of SPP200A, SPP400A, and SPP800A thermosensitive conductive hydrogels in PBS; (D) In ​​vitro degradation curves of SPP200A, SPP400A, and SPP800A thermosensitive conductive hydrogels in PBS containing lysozyme; (E) Tensile stress-strain curves of SPP200A, SPP400A, and SPP800A thermosensitive conductive hydrogels; (F) Water contact angle test of hydrophilic and hydrophobic surfaces of the hydrovoltaic layer (porous carbon film).

[0027] Figure 6 In vitro cell experiments were conducted to characterize the hydrovoltaic battery dressing of this invention. Note: (A) Live and dead cell staining of SPP200A, SPP400A, and SPP800A thermosensitive conductive hydrogels (scale bar: 200 μm); (B) Cytoskeleton staining of SPP200A, SPP400A, and SPP800A thermosensitive conductive hydrogels (scale bar: 50 μm); (C) Cell scratch assay of SPP200A, SPP400A, and SPP800A hydrovoltaic battery dressings; (D) Intracellular reactive oxygen species probe staining of SPP200A, SPP400A, and SPP800A hydrovoltaic battery dressings (scale bar: 100 μm); (E) MTT assay of SPP200A, SPP400A, and SPP800A thermosensitive conductive hydrogels; (F) Intracellular ATP content assay of SPP200A, SPP400A, and SPP800A hydrovoltaic battery dressings.

[0028] Figure 7 Evaluation of the wound healing effect of the hydrovoltaic battery dressing of the present invention in rats; Note: (A) Gross wound healing of the Control, 3M, SPP800A hydrogel, and SPP800A battery groups; (CD) Wound healing rate of the Control, 3M, SPP800A hydrogel, and SPP800A battery groups.

[0029] Figure 8 Histological staining of wound healing in rats using the hydrovoltaic battery dressing of the present invention; Note: (A) H&E staining of Control, 3M, SPP800A hydrogel, and SPP800A battery groups (scale bar: 500 μm); (B) Quantitative analysis of collagen deposition area of ​​Control, 3M, SPP800A hydrogel, and SPP800A battery groups; (C) Masson staining of Control, 3M, SPP800A hydrogel, and SPP800A battery groups (scale bar: 200 μm).

[0030] Figure 9 Immunohistochemical staining of wound tissue for the hydrovoltaic battery dressing of the present invention; Note: Representative staining images of TNF-α, IL-6, EGF, CD31, TGF-β, and α-SMA in (AF) Control, 3M, SPP800A hydrogel, and SPP800A battery groups (scale bar: 100 μm).

[0031] Figure 10 For quantitative analysis of immunohistochemical staining of wound tissue in the hydrovoltaic battery dressing of the present invention; Note: Semi-quantitative analysis statistics of TNF-α, IL-6, EGF, CD31, TGF-β, and α-SMA in (AF) Control, 3M, SPP800A hydrogel, and SPP800A battery groups. Detailed Implementation

[0032] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0033] It should be noted that, unless otherwise specified, the methods described in the following embodiments are all conventional methods, and the reagents described are all commercially available.

[0034] It should be noted that, in this invention, the indications related to skin injury include: (1) Physical injury Mechanical injuries: abrasions, cuts, lacerations, pressure sores (pressure injuries).

[0035] Temperature-related injuries: burns (flames, hot liquids), scalds, frostbite.

[0036] Radiation injury: radiation dermatitis (common after tumor radiotherapy).

[0037] Photosensitive damage: acute sunburn, chronic actinic dermatitis.

[0038] (2) Infectious skin lesions Bacterial infections: cellulitis, erysipelas, impetigo, folliculitis, boils and carbuncles, and wounds with secondary infections.

[0039] Viral: Herpes simplex (HSV), herpes zoster (varicella-zoster virus), chickenpox (severe cases may involve skin ulceration).

[0040] Fungal infections: tinea corporis, tinea cruris, tinea manuum and tinea pedis (when accompanied by maceration and erosion), and candidal intertrigo.

[0041] Parasites / insects: scabies (due to skin damage from scratching), secondary infection of insect bite dermatitis.

[0042] (3) Allergic reactions and immune damage Contact dermatitis: Acute redness, swelling, blisters, and erosion caused by chemicals, topical medications, cosmetics, etc.

[0043] Atopic dermatitis (eczema): Acute phase is accompanied by exudation and erosion.

[0044] Autoimmune bullous diseases: pemphigus, pemphigoid (characterized by skin and mucous membrane vesicles and erosions, which are severe skin lesions).

[0045] Drug eruption: Severe drug eruptions, such as Stevens-Johnson syndrome (SJS) and toxic epidermal necrolysis (TEN), are characterized by large-area epidermal loosening and shedding, and are classified as acute and critical illnesses.

[0046] (4) Vascular and metabolic damage (chronic, non-healing wounds) Vascular ulcers: varicose ulcers (usually located above the medial malleolus) and arteriosclerotic ulcers (usually located at the extremities, such as the toes).

[0047] Diabetic foot: Foot ulcers and gangrene caused by diabetic neuropathy and vascular disease.

[0048] Gangrene: dry gangrene, wet gangrene (usually caused by severe ischemia or infection).

[0049] (5) Tumor-related skin lesions Malignant skin tumors: basal cell carcinoma (BCC), squamous cell carcinoma (SCC), melanoma, etc., often show ulceration, necrosis, and bleeding in the center of the tumor.

[0050] Cancerous ulcer: Ulceration caused by invasion of the skin by primary or metastatic tumors (mycosis / mycosis granuloma, etc.).

[0051] (6) Special populations and iatrogenic injury Newborns: Neonatal diaper dermatitis (with erosion in severe cases), bullous epidermolysis (hereditary disease).

[0052] Surgery-related: poor wound healing, wound infection, wound dehiscence.

[0053] Peristostomy skin: peristomal dermatitis and ulceration.

[0054] (7) Secondary damage to chronic pruritus Examples include nodular prurigo and neurodermatitis (prolonged scratching leading to lichenification of the skin, epidermal peeling, and bleeding).

[0055] Example 1: Preparation of Thermosensitive Conductive Hydrogel (1) Take 2 g of sodium alginate, 20 g of N-isopropylacrylamide, 0.1 g of N,N-methylenebisacrylamide, 0.1 g of acrylamide phenylboronic acid and 0.4 g of photoinitiator 2959 respectively, dissolve them in 100 ml of deionized water, stir magnetically at room temperature for 6-12 h until uniform and transparent, then pass high-purity nitrogen gas for 20-60 min to remove dissolved oxygen, and obtain sodium alginate / N-isopropylacrylamide sol; (2) Take three 10 ml portions of sodium alginate / N-isopropylacrylamide sol obtained in step (1), and add 200 μL, 400 μL, and 800 μL of PEDOT / PSS aqueous dispersion (purchased from Xi'an Yuri Solar Energy Technology Co., Ltd., model FY-800, concentration 1.5 wt%) to them respectively. Vortex for 2-5 min until evenly mixed to obtain three portions of sodium alginate / N-isopropylacrylamide / PEDOT / PSS sol. Among them, the sodium alginate / N-isopropylacrylamide / PEDOT / PSS sol with a volume of 200 μL of PEDOT / PSS aqueous dispersion is named SPP200A sol, the sodium alginate / N-isopropylacrylamide / PEDOT / PSS sol with a volume of 400 μL of PEDOT / PSS aqueous dispersion is named SPP400A sol, and the sodium alginate / N-isopropylacrylamide / PEDOT / PSS sol with a volume of 800 μL of PEDOT / PSS aqueous dispersion is named SPP400A sol. The μL sodium alginate / N-isopropylacrylamide / PEDOT / PSS sol was named SPP800A sol. (3) Pour the three portions of sodium alginate / N-isopropylacrylamide / PEDOT / PSS sol obtained in step (2) into polytetrafluoroethylene molds with a diameter of approximately 9 cm, and control the temperature using an ice-water bath. The light intensity is 10 mW / cm² at a center wavelength of 365 nm. 2 Vertical irradiation under ultraviolet light for 30-60 minutes initiates a free radical copolymerization reaction, forming a primary hydrogel network mainly composed of covalent cross-links.

[0056] (4) Take the nascent hydrogel obtained in step (3) out of the mold and immerse it in a 1 wt% CaCl2 solution for 5-30 min. It will undergo ion coordination with the carboxyl groups on sodium alginate to form a second physical cross-linking network, thereby improving the mechanical stability of the hydrogel.

[0057] (5) The hydrogel obtained in step (4) is placed in a large amount of deionized water and soaked and washed at 4°C. The soaking solution is changed every 8 h for 24 h to remove unreacted monomers, initiator residues and excess ions, so as to obtain sodium alginate / N-isopropylacrylamide / PEDOT / PSS sol hydrogel, which is the designed temperature-sensitive conductive hydrogel. Among them, the sodium alginate / N-isopropylacrylamide / PEDOT / PSS hydrogel with a PEDOT / PSS aqueous dispersion volume of 200 μL is named SPP200A hydrogel, the sodium alginate / N-isopropylacrylamide / PEDOT / PSS hydrogel with a PEDOT / PSS aqueous dispersion volume of 400 μL is named SPP400A hydrogel, and the sodium alginate / N-isopropylacrylamide / PEDOT / PSS hydrogel with a PEDOT / PSS aqueous dispersion volume of 800 μL is named SPP800A hydrogel.

[0058] Example 2: Preparation of a hydrovoltaic power generation layer (porous carbon film) with a wettability gradient (1) Take 0.1 g of carbon black nanopowder (particle size 10-100 nm), add it to 10 mL of anhydrous ethanol, put it in an ice water bath, and treat it for 30 min using an ultrasonic cell disruptor (power 300 W, working for 2 s, intermittent for 1 s) to obtain a uniform and stable carbon black ethanol dispersion. (2) Take a qualitative filter paper with a diameter of 125 mm (pore size of about 20-25 μm), lay it flat on a clean glass plate, and use a pipette to evenly and slowly drop the carbon black ethanol dispersion obtained in step (1) onto the entire surface of the filter paper. Then transfer it to a 70°C drying oven and dry it for 0.5-1 h to obtain the carbon black hydrophilic layer of the hydrovoltaic power generation layer (porous carbon membrane). (3) Flip the hydrophilic carbon black layer of the water-voltaic power generation layer (porous carbon film) obtained in step (2) so that the side without carbon black layer is facing up. Sprinkle a layer of microcrystalline paraffin powder evenly on its surface, so that the amount of paraffin on this side surface is 0.5-1 g / cm². Put it in a 70°C oven again and heat for 4 min until the paraffin is completely melted and forms a continuous and smooth film. Cool it naturally to room temperature to obtain the hydrophobic paraffin layer of the water-voltaic power generation layer (porous carbon film). Together with the hydrophilic carbon black layer of the water-voltaic power generation layer (porous carbon film) obtained in step (2), they are assembled into a water-voltaic power generation layer (porous carbon film) with a wettability gradient.

[0059] Example 3: Assembly and Packaging of Hydrovoltaic Battery Dressing (1) Cut the hydrovoltaic power generation layer (porous carbon film) prepared in Example 2 into a rectangular sheet of 3.0 cm × 2.0 cm. On its hydrophilic surface (carbon black surface), along the long axis, about 0.5 cm from both ends, firmly attach a piece of carbon cloth (as cathode) of size 1.5 cm × 0.8 cm and a piece of zinc foil of the same size (as anode) with conductive copper tape. In order to fix the electrode materials more firmly, the conductive copper tape extends across the carbon black surface to the paraffin surface. (2) Cut the thermosensitive conductive hydrogel prepared in Example 1 into a thin sheet with a size of about 1.5 cm × 0.8 cm × 2 cm and use it as a solid electrolyte / ion conduction layer. Use sterile filter paper to gently absorb the excess free water on the surface of the hydrogel and attach it to the hydrophilic surface of the water-voltaic power generation layer (porous carbon film) with the electrodes installed in step (1), ensuring that it completely covers the area between the two electrodes and is fully attached to the carbon cloth and the electrodes to obtain the assembly. (3) The assembly obtained in step (2) is encapsulated with a 100 μm thick transparent polyethylene terephthalate (PET) film with good biocompatibility. A square window of 1.5 cm × 1.5 cm (first window) is cut out on the PET film directly above the hydrogel area. A window of the same size (second window) is also cut out on the PET film corresponding to the other side of the assembly (i.e., the hydrophobic surface of the hydrovoltaic power generation layer (porous carbon film)). The edges of the PET film are sealed with staples to obtain the final hydrovoltaic battery dressing. The hydrovoltaic battery dressing assembled with SPP200A hydrogel is named SPP200A hydrovoltaic battery dressing, the hydrovoltaic battery dressing assembled with SPP400A hydrogel is named SPP400A hydrovoltaic battery dressing, and the hydrovoltaic battery dressing assembled with SPP800A hydrogel is named SPP800A hydrovoltaic battery dressing.

[0060] like Figure 1 As shown, the layer structure and material composition of the hydrovoltaic battery dressing are clearly demonstrated, and the hydrovoltaic battery dressing was successfully constructed.

[0061] Example 4: Electrical Output and Stability Characterization of Water-Based Battery Dressing This experiment uses the various water-voltaic battery dressings prepared in Example 3 as the subjects for the following experiments: (1) The various water-volt battery dressings prepared in Example 3 were placed at a constant temperature of 37°C (in vitro simulated environment) and on the full-thickness skin defect wound on the back of a live SD rat (see Example 7 for animal model). The output current was recorded in real time in short-circuit mode using a Keithley DMM6500 high-precision digital multimeter. like Figure 2 As shown in (AC), under in vitro simulation conditions, the peak output current of the prepared hydrovoltaic battery dressing increases with the increase of the volume of the PEDOT / PSS aqueous dispersion. The SPP800A hydrovoltaic battery dressing can generate a peak short-circuit current of approximately 340 μA, and the high current output can be sustained for approximately 8 hours. Figure 2 (D) Compared to animal models, the SPP800A hydrocell dressing can also generate a continuous and abundant output current to meet the needs of promoting wound healing.

[0062] (2) Connect the eight SPP800A water-volt battery dressings prepared in Example 3 in series and measure the open circuit voltage using a Keithley DMM6500 high-precision digital multimeter; like Figure 3As shown, the total open-circuit voltage of the series circuit is approximately 4.5 V, which can successfully light up a standard red LED bulb and make it emit light stably, and can also drive a solar-powered calculator to work normally.

[0063] (3) Using a CHI 760E electrochemical workstation, electrochemical impedance spectroscopy (EIS) was performed on various water-voltaic battery dressings prepared in Example 3 in the frequency range of 0.01 Hz-100 kHz. like Figure 4 As shown in (A), as the volume of the PEDOT / PSS aqueous dispersion increases, the relevant equivalent resistance of the prepared water-voltaic battery dressing decreases significantly and the conductivity increases.

[0064] (4) The various water-voltaic battery dressings prepared in Example 3 were subjected to drying-rehydration cycles (dried in a 60°C oven to constant weight, and then immersed in 37°C PBS for 2 h for rehydration), and the water absorption rate after each cycle was recorded and electrochemical impedance spectroscopy (EIS) was performed. like Figure 4 As shown in (DE), after 30 days (approximately 15 cycles), the water absorption rate of various water-based battery dressings remained stable (approximately 950-1050%), and the internal resistance showed a decreasing trend, indicating good cycle stability and reliable "self-regeneration" capability, suggesting the feasibility of long-term operation.

[0065] Example 5: Characterization of the basic physicochemical properties of the temperature-sensitive conductive hydrogel and the hydrovoltaic power generation layer (porous carbon film) of the hydrovoltaic battery dressing. This experiment uses the various temperature-sensitive conductive hydrogels and water-voltaic power generation layers (porous carbon films) prepared in Examples 1 and 2 as the subjects for the following experiments: (1) The microstructure of the SPP800A thermosensitive conductive hydrogel prepared in Example 1 and the water-voltaic power generation layer (porous carbon film) prepared in Example 2 were characterized by scanning electron microscopy (SEM). (2) The chemical composition of the SPP800A thermosensitive conductive hydrogel prepared in Example 1 was characterized by Fourier transform infrared spectroscopy (FTIR); like Figure 4 As shown in (BC), the SPP800A thermosensitive conductive hydrogel has an interconnected porous structure with a pore size of about 50-200 μm, and the hydrovoltaic layer (porous carbon film) also has a nano- to micron-level multi-level pore structure on its surface. like Figure 5 As shown in (A), the SPP800A thermosensitive conductive hydrogel contains characteristic absorption peaks of the components involved, indicating that the components were successfully introduced and coexist.

[0066] (3) The water content, swelling ratio and in vitro degradation rate of various temperature-sensitive conductive hydrogels prepared in Example 1 were determined by weighing method; like Figure 5 As shown in (BD), the SPP800A thermosensitive conductive hydrogel has a high water content (>90%) and a high swelling ratio (approximately 1000%), and exhibits controlled degradation behavior over a period of 21 days, with a mass reduction of approximately 40%.

[0067] (4) The tensile properties of various temperature-sensitive conductive hydrogels prepared in Example 1 were characterized by using a universal testing machine; like Figure 5 As shown in (E), the tensile properties of the various thermosensitive conductive hydrogels prepared meet the requirements of dressing applications.

[0068] (5) The wettability of both sides of the water-voltaic power generation layer (porous carbon film) prepared in Example 2 was characterized by a contact angle measuring instrument; like Figure 5 As shown in (F), there is a significant difference in wettability on both sides of the prepared hydrovoltaic power generation layer (porous carbon film), which can form a wettability gradient structure.

[0069] Example 6: Characterization of the cell compatibility of thermosensitive conductive hydrogels and the cellular behavioral regulation of hydrovoltaic battery dressings This experiment uses the various temperature-sensitive conductive hydrogels and water-volt battery dressings prepared in Examples 1 and 3 as the subjects for the following experiments: (1) Various temperature-sensitive conductive hydrogels prepared in Example 1 were co-cultured with L929 cells (purchased from Wuhan Zishan Biotechnology, catalog number STCC20025) in 12-well plates. After the set culture time, the cells were stained with a live-dead cell staining kit (A084A241127, Beyotime, China) for 0.5 h. Then the staining solution was removed to terminate the incubation. An appropriate amount of PBS was added to cover the cells. Live cells (green fluorescence) and dead cells (red fluorescence) were photographed using an inverted fluorescence microscope (VERT1, Zeiss, USA). (2) Various thermosensitive and conductive hydrogels prepared in Example 1 were co-cultured with L929 cells in a laser confocal dish. After the culture time was set, the cells were stained with a cytoskeleton staining kit (23122, AAT Bioquest, USA) for 1 h. Then the staining solution was removed to terminate the incubation. An appropriate amount of PBS was added to cover the cells, and the cell morphology was observed by a laser confocal scanning microscope (LSM 900, Zeiss, USA). like Figure 6 As shown in (AB), most of the live cells were stained green, and a very small number of dead cells were stained red. The cells in each group had good morphology, indicating that the various types of thermosensitive conductive hydrogels prepared were non-cytotoxic.

[0070] (3) The effects of cell scratch assay on the regulation of cell migration behavior of various water-voltaic battery dressings prepared in Example 3 were evaluated. L929 cells were cultured in 6-well plates until the cell confluence rate reached 90%. Cell-free areas were marked out using pipette tips. Each group of samples, which had been strictly sterilized, were co-cultured with cells. Stimulation was performed for 15 min every day. Cells were cultured in serum-free medium to eliminate the influence of serum. After the set time, 4% paraformaldehyde buffer was added and fixed at room temperature for 15 min. The cells were washed 2-3 times with PBS, then stained with 0.1% crystal violet solution for 15 min, and washed 2-3 times with PBS. Finally, the cell scratch healing was photographed and observed using an inverted fluorescence microscope (Nikon-ECLIPSE 80i / DS-Ri2 / NIS-ElementsD, Nikon, Japan).

[0071] like Figure 6 As shown in (C), under electrical stimulation, the migration speed of L929 cells to the scratch area was significantly accelerated, and the cells in the SPP800A group that released the maximum electrical stimulation migrated the fastest.

[0072] (4) The intracellular ROS scavenging ability of various hydrovoltaic battery dressings prepared in Example 3 was evaluated by intracellular reactive oxygen species (ROS) probe staining. L929 cells were seeded in 6-well plates and cultured until the cell confluence reached 50%-70% at the time of the experiment. The ROS detection kit (G1706-100T, Servicebio, China) was used for testing. The core of the kit is the fluorescent probe DCFH-DA. First, the cells were treated with 100 μM H2O2 for 60 min to stimulate cell damage. Then, the hydrovoltaic battery was connected to the cells with silver wire and co-cultured for 24 h. Before the samples were collected, the probe was loaded. The positive control for increased ROS was that the cells were treated with 100 μM H2O2 for 60 min and the DCFH-DA probe was diluted with serum-free culture medium at a ratio of 1:1000 to make the final concentration 10. μM / L, remove the original culture medium from the cell culture plate, gently wash the cells once with PBS to remove residual serum and drug interference, add diluted DCFH-DA working solution to fully cover the cells, place the culture plate in a 37℃ cell culture incubator and incubate in the dark for 30 min, discard the probe working solution, wash the cells 2-3 times with PBS to fully remove DCFH-DA that has not entered the cells and reduce background fluorescence interference, place the washed cells directly under an inverted fluorescence microscope (CNikon-ECLIPSE 80i / DS-Ri2AIS-ElementsD, Nikon, Japan), use excitation light of about 488 nm wavelength, and observe the emission light of about 525 nm (FITC channel). like Figure 6As shown in (D), under electrical stimulation, the fluorescence intensity of intracellular reactive oxygen species probes in each group of cells decreased significantly, approaching normal levels, suggesting that the various types of hydrovoltaic battery dressings prepared can effectively reduce intracellular ROS levels and alleviate oxidative stress damage by releasing electrical stimulation.

[0073] (5) Various temperature-sensitive conductive hydrogels prepared in Example 1 were co-cultured with L929 cells. The cells were cultured in high-glucose DMEM supplemented with 10% fetal bovine serum and 1% penicillin / streptomycin. After the set time, an appropriate amount of MTT reagent (MB4698, MEILUNE, China) was added and incubated at 37°C for 4 h. Then the supernatant was removed, and dimethyl sulfoxide was added to dissolve the purple crystals formed. The solution was shaken at room temperature in the dark for 10 min to dissolve the crystals evenly. Finally, the solution was transferred to a 96-well plate and the absorbance value was read at 490 nm using an ELISA reader (Infinite M Nano, TECAN, China). Each group was repeated three times. like Figure 6 As shown in (E), the cell survival rate of each group is >90%, indicating that the various types of thermosensitive conductive hydrogels prepared are non-cytotoxic.

[0074] (6) The intracellular ATP generation capacity of various water-voltaic battery dressings prepared in Example 3 was evaluated by using an ATP detection kit (S0027, Beyotime, China). The samples were co-cultured with L929 cells. After the culture time was set, the concentration of ATP generated by each group of cells was determined by using the ATP concentration detection standard curve. Then, the protein concentration detection kit (AR0145, BOSTER, China) was used for normalization. like Figure 6 As shown in (F), under electrical stimulation, the intracellular ATP production of cells in each group increased, suggesting that the various types of hydrovoltaic battery dressings prepared can promote the increase of ATP synthesis by releasing electrical stimulation, thus providing energy for cell behavior regulation.

[0075] Example 7: Characterization of wound healing efficacy of hydrovoltaic battery dressing This experiment uses the SPP800A temperature-sensitive conductive hydrogel and the water-voltaic battery dressing prepared in Examples 1 and 3 as the subjects for the following experiments: (1) All experiments were conducted with the approval of the animal ethics committee. Healthy female SD rats weighing 160-200 g were selected for the experiment. Three parallel groups were set up. After strict anesthesia, analgesia, disinfection, and hair removal, a full-thickness skin defect model of the rat back was constructed using a 10 mm diameter circular punch. Subsequently, the strictly sterilized samples of each group were covered on the wound and fixed on the normal skin on both sides of the wound. Different experimental groups were set up: (I) Blank control group (no cover), named Control; (II) 3MTM Tegaderm TM The dressing group (purchased from Minnesota Mining Manufacturing Medical Devices Co., Ltd., Shanghai Medical Device Registration Certificate 20202140570) was named 3M; (III) SPP800A temperature-sensitive conductive hydrogel group (only temperature-sensitive conductive hydrogel was applied) was named SPP800A hydrogel; (IV) SPP800A water-volt battery dressing group was named SPP800A battery. After the set number of days of treatment, the wound area of ​​each group was photographed and measured to assess the wound healing status. like Figure 7 As shown in AC, the SPP800A battery group had the fastest healing speed, with a wound closure rate of 98.4% ± 1.2% on day 14, which was significantly higher than that of the SPP800A hydrogel group (92.1% ± 2.5%), the 3M group (85.0% ± 3.1%), and the Control group (80.5% ± 4.3%).

[0076] (2) After the set number of days of treatment, the corresponding number of rats were euthanized, and tissue specimens from the wound area of ​​each group were collected, fixed with 4% paraformaldehyde buffer, and then subjected to gradient dehydration, paraffin embedding and sectioning in sequence. Subsequently, the sections of each group were subjected to H&E, Masson and immunohistochemical staining, and the histological healing was observed and evaluated using an optical microscope. like Figure 8 As shown in AC, the SPP800A battery group showed complete epidermal regeneration, regular dermal structure, minimal inflammatory cell infiltration, and richer collagen deposition at all stages of healing. Furthermore, the collagen fibers were more densely and orderly arranged on day 14, resulting in the best healing quality. like Figure 9 As shown in AF and 10A-F, the expression levels of TNF-α and IL-6 in the SPP800A battery group were significantly lower than those in other groups in the early stages (days 4 and 7); the expression of EGF and CD31 reached its peak on day 7 and was significantly higher than that in other groups; and it could dynamically regulate the expression of TGF-β and α-SMA: moderately upregulated during the proliferation phase (day 7) to promote repair, while downregulated more promptly and significantly during the remodeling phase (day 14) to avoid excessive fibrosis and promote functional regeneration; suggesting that the SPP800A hydrovoltaic battery dressing can promote inflammation regulation, angiogenesis, re-epithelialization and tissue remodeling by releasing electrical stimulation, thereby promoting rapid wound healing.

[0077] In summary, this invention successfully designed and constructed a self-powered hydrovoltaic battery dressing with both autonomous water release and replenishment functions. This dressing innovatively integrates a temperature-sensitive conductive hydrogel layer and a hydrovoltaic power generation layer, achieving adaptive and self-sustaining intervention of the wound microenvironment. Through a unique "water storage-release-replenishment" closed-loop mechanism, the system utilizes body temperature to trigger on-demand water release and absorbs tissue exudate and water from the external aquatic environment to achieve self-replenishment of fuel and energy recycling. This overcomes the technical bottlenecks of unstable energy sources and intermittent supply in existing self-powered systems, ensuring continuous and stable therapeutic electrical stimulation throughout the entire healing cycle. More importantly, this self-generated electrical signal can intelligently couple with the physiological state of the wound and the healing process, temporally regulating key aspects such as inflammation resolution, angiogenesis, and tissue remodeling at the molecular and cellular levels. Animal experiments have confirmed that, compared to traditional treatment methods, this dressing can significantly accelerate wound closure and promote orderly and high-quality regeneration and repair. Therefore, this invention not only provides a novel treatment solution for chronic, difficult-to-heal wounds that requires no external power source, is easy to use, and has a clear therapeutic effect, but also provides a new paradigm for integrated device design in the field of tissue repair and regenerative medicine that combines intelligent response and active treatment functions.

[0078] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, and not to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some or all of the technical features; and these modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A self-powered hydrovoltaic battery dressing with both self-releasing and self-replenishing water functions, characterized in that, The self-powered hydrovoltaic battery dressing includes a hydrophilic layer and a hydrophobic layer disposed on both sides of a square filter paper. A cathode and an anode are disposed at opposite ends of the hydrophilic layer. A temperature-sensitive conductive hydrogel is covered between the cathode and the anode. The dressing is then encapsulated with a thin film, with windows opened on both sides of the film. The thermosensitive conductive hydrogel is obtained by adding PEDOT / PSS aqueous dispersion to a mixed solution of sodium alginate, N-isopropylacrylamide, N,N-methylenebisacrylamide, acrylamide phenylboronic acid and photoinitiator, followed by photocrosslinking and then chemical crosslinking.

2. The self-powered hydroelectric battery dressing as described in claim 1, characterized in that, The addition ratios of sodium alginate, N-isopropylacrylamide, N,N-methylenebisacrylamide, acrylamide-phenylboronic acid, and photoinitiator are 2:20:0.1:0.1:0.4, respectively.

3. The self-powered hydroelectric battery dressing as described in claim 1, characterized in that, The addition ratio of the PEDOT / PSS aqueous dispersion is 0.02-0.08:

100.

4. The self-powered hydroelectric battery dressing as described in claim 1, characterized in that, The hydrophilic layer is obtained by coating the filter paper surface with a carbon black ethanol dispersion, and the hydrophobic layer is obtained by coating the filter paper surface with paraffin wax.

5. The self-powered hydroelectric battery dressing as described in claim 1, characterized in that, The film is a polyethylene terephthalate film.

6. The self-powered hydroelectric battery dressing as described in claim 1, characterized in that, The temperature-sensitive conductive hydrogel is prepared by the following method: (1) Sodium alginate, N-isopropylacrylamide, N,N-methylenebisacrylamide, acrylamide phenylboronic acid and photoinitiator 2959 were dissolved in deionized water and stirred at room temperature until they were uniform and transparent. High-purity nitrogen was introduced to remove dissolved oxygen to obtain sodium alginate / N-isopropylacrylamide sol. (2) Take the sodium alginate / N-isopropylacrylamide sol obtained in step (1), add PEDOT / PSS aqueous dispersion to it, shake until it is mixed evenly, and obtain sodium alginate / N-isopropylacrylamide / PEDOT / PSS sol; (3) Pour the sodium alginate / N-isopropylacrylamide / PEDOT / PSS sol obtained in step (2) into a polytetrafluoroethylene mold, control the temperature in an ice water bath, and irradiate with ultraviolet light to form a nascent hydrogel network. (4) Remove the nascent hydrogel network obtained in step (3) from the mold and immerse it in CaCl2 solution for 5-30 minutes; (5) Place the hydrogel obtained in step (4) in deionized water and soak and wash it to obtain a temperature-sensitive conductive hydrogel.

7. The self-powered hydroelectric battery dressing as described in claim 6, characterized in that, The ultraviolet light in step (3) has a center wavelength of 365 nm and a light intensity of 10 mW / cm. 2 .

8. The self-powered hydroelectric battery dressing as described in claim 6, characterized in that, The concentration of the CaCl2 solution in step (4) is 1 wt.

9. The use of the self-powered hydrovoltaic battery dressing as described in any one of claims 1-8 in the preparation of products for the prevention and / or treatment of indications related to skin lesions.

10. A dressing for repairing skin damage, characterized in that, The dressing comprises the self-powered hydrovoltaic battery dressing according to any one of claims 1-8, or is prepared from the self-powered hydrovoltaic battery dressing according to any one of claims 1-8.

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