Preparation method of self-healing hydrogel with sensing and antibacterial functions
By preparing Ag@PDA NPs/AM/SBMA/CNF hydrogels, the problems of pain and cracking during hydrogel dressing changes were solved, realizing a multifunctional hydrogel with self-healing, antibacterial and sensing functions, suitable for stable adhesion and motion monitoring of different parts of the human body.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2026-04-16
- Publication Date
- 2026-06-26
AI Technical Summary
Existing hydrogel dressings are prone to causing pain, adhesion, and cracking to the injured when they are changed. They also have poor sensing and antibacterial effects, are complex to manufacture, costly, and difficult to achieve high adhesion, self-healing and real-time monitoring functions.
A multifunctional hydrogel with self-healing, antibacterial, and sensing functions was prepared by using Ag@PDA NPs/AM/SBMA/CNF hydrogels through dynamic interactions of covalent and non-covalent bonds, combined with the synergistic effect of Ag and SBMA. The preparation process was simplified by using UV-initiated self-polymerization technology.
It achieves rapid self-healing, excellent antibacterial properties, high adhesion and real-time sensing capabilities, and is suitable for stable fit and motion monitoring in different parts of the human body, especially joints, with highly efficient antibacterial and sensing performance.
Smart Images
Figure FT_1
Abstract
Description
Technical Field
[0001] This invention belongs to the field of biomaterial preparation, and designs a method for preparing a multifunctional hydrogel with high adhesion, self-healing and electrostimulation antibacterial properties that combines sensing and antibacterial functions. Background Technology
[0002] Skin is the primary physical barrier between the human body and the environment. Skin injuries are easily infected by bacteria, leading to fluid loss and various complications that can affect health and even endanger life. Although traditional wound dressings such as gauze, bandages, and membranes have been developed and used in clinics, they still suffer from limitations such as limited functionality, secondary injury during dressing changes, and the potential for inflammation. In practical applications, ideal dressings should meet requirements such as maintaining a moist environment, enhancing epidermal migration, promoting angiogenesis, being adhesive and easily removable, preventing bacterial infection, and being suitable for different areas. Hydrogel dressings, with their rich 3D structure and ability to promote cell hydration and gas and nutrient exchange, provide a moist environment for cell growth, proliferation, and migration, accelerating wound healing. As a biomaterial most similar to living tissue, hydrogels can directly contact human tissue, preventing external microbial infection, effectively preventing fluid loss, and transporting oxygen, thus promoting wound healing. Due to their excellent biochemical and mechanical properties, hydrogels have become one of the most competitive candidate materials in the field of wound dressings in recent decades, showing a growing trend year by year and demonstrating a bright future.
[0003] Designing and functionalizing hydrogels through physical and chemical cross-linking to create multifunctional hydrogel dressings has been a persistent pursuit. Among these, sensing hydrogels specifically recognize external physical stimuli or chemical molecular signals. Leveraging the highly efficient conduction properties of zwitterions, they convert external stimuli into detectable electrical signal changes in real time. Stable signal output and feedback are achieved through rapid-response ion transport pathways, enabling real-time monitoring of target parameters. However, developing a multifunctional hydrogel dressing that combines sensing and antibacterial effects with high adhesion, self-healing properties, real-time wound dynamic monitoring, and biocompatibility remains a significant challenge. While current hydrogel dressings can fill wounds without adhering to them, dressing changes still cause pain, especially for large wounds where dressing changes are lengthy, placing a considerable psychological burden on patients. Furthermore, hydrogel dressings are prone to cracking, breakage, and aging under stress and strain, damaging the gel's network structure and degrading its performance, thus limiting its applications. In addition, most studies on the design of hydrogel dressings mainly consider mechanical properties and biocompatibility, but there are relatively few strategies for sensing physiological motion signals. Furthermore, hydrogel dressings suffer from problems such as complex manufacturing processes, high costs, poor antibacterial effects, and unsatisfactory sensing performance, which limit their further application. Summary of the Invention
[0004] To address the shortcomings of existing technologies, this invention provides a method for preparing a multifunctional hydrogel dressing with synergistic sensing and antibacterial effects, exhibiting high adhesion, self-healing properties, electrostimulation-induced antibacterial activity, and real-time wound healing monitoring. This invention uses an acrylamide (AM) and 2-(methacryloyloxy)ethyldimethyl-(3-sulfopropyl)ammonium hydroxide (SBMA) solution with cellulose nanofibers (CNF) as the hydrogel substrate, silver@polydopamine nanoparticles (Ag@PDA NPs) as the nanoparticles, 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylphenylacetone (I2959) as the photoinitiator, and polyethylene glycol diacrylate (PEGDA) as the crosslinking agent. Ultraviolet light-initiated self-polymerization is employed to prepare a smart Ag@PDA NPs / AM / SBMA / CNF hydrogel with multiple dynamically reversible bonds. The preparation method of this invention is simple and easy to operate. By constructing various dynamic reversible interactions, including covalent and non-covalent bonds and interionic interactions, a self-healing Ag@PDA NPs / AM / SBMA / CNF hydrogel was obtained. Ag and DA were introduced to prepare Ag@PDA with antibacterial, adhesive, and electronic conductivity properties, while zwitterionic SBMA was introduced to provide ionic conductivity. The synergistic effect of these two compounds endows the hydrogel with conductivity. The hydrogel prepared by this method can achieve rapid sterilization while possessing excellent biocompatibility, high adhesion, antibacterial properties, sensing capabilities, and environmental adaptability. It can be used in antibacterial dressings to promote wound healing and in flexible sensors.
[0005] The present invention discloses a method for preparing a self-healing hydrogel with both sensing and antibacterial properties, comprising the following steps:
[0006] (1) Add a certain mass ratio of dopamine hydrochloride (DA) to a Tris alkaline solution, centrifuge and stir to form a suspension. Add a certain amount of ammonium hydroxide (NH4OH) solution, silver nitrate (AgNO3) solution and deionized water to a beaker, and form a mixed solution of a certain concentration at 25°C. The solution first produces a brown precipitate and then the precipitate disappears. The solution is then completely protected from light. At the same time, add the above suspension to the mixed solution and react for a certain time to form silver@polydopamine nanoparticles (Ag@PDA NPs).
[0007] (2) Take a certain mass of cellulose nanofibers (CNF) and deionized water and add them to a beaker. At a temperature of 25°C, a CNF solution is formed. Take a certain mass ratio of acrylamide (AM) and 2-(methacryloyloxy)ethyldimethyl-(3-sulfopropyl)ammonium hydroxide (SBMA) monomers and add them to the CNF solution. Mix them evenly to form a transparent solution.
[0008] (3) Finally, a certain amount of crosslinking agent, an appropriate amount of photoinitiator, and Ag@PDA NPs of different mass ratios were added to the above system using ultraviolet light-initiated self-polymerization technology. After reacting for a period of time, Ag@PDA NPs / AM / SBMA / CNF hydrogel was obtained.
[0009] Preferably, in step (1), the mass ratio of tris base to dopamine hydrochloride (DA) is 1:1 to 5:1, and the reaction time is 20 to 30 hours.
[0010] Preferably, in step (2), the mass concentration of CNF is 1~10wt%, and the mass ratio of AM:SBMA:CNF is 7:14~34wt%:5~12wt%.
[0011] Preferably, in step (3), the crosslinking agent is one or more of polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, N,N'-methylenebisacrylamide, ethylene glycol dimethacrylate, etc., and the amount of the crosslinking agent is 0.5~2wt% of the monomer mass; the photoinitiator is one or more of 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylphenylacetone, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, etc., and the amount of the photoinitiator is 0.5~3wt% of the total monomer mass, and the mass ratio of Ag@PDA NPs is 0.25~2wt% of the total mass of AM and SBMA.
[0012] Preferably, the Ag@PDA NPs / AM / SBMA / CNF hydrogel is suitable for electrostimulation antibacterial and real-time monitoring of human dynamics.
[0013] Compared with the prior art, the beneficial effects of the present invention are:
[0014] (1) The preparation method of the present invention is simple, the materials are easy to obtain, the operation is convenient, and the conditions are mild, which solves the problems of complex preparation process and harsh conditions required in existing gel dressings.
[0015] (2) A rapidly self-healing Ag@PDANPs / AM / SBMA / CNF hydrogel was obtained by utilizing various covalent and non-covalent bonds such as ionic bonds, hydrogen bonds, and double bonds, which solved the problems of cracking, breakage, and aging that easily occur under stress-strain conditions during use. After the gel is cut, it can achieve self-healing within 1 minute, and deformation will occur at 620% of the damage deformation point. Its mechanical properties that match the skin make it easy to replace and fix. It is especially suitable for attaching to the finger joints of the human body. It can maintain good fit and response stability during different flexion and extension angles and dynamic bending processes, thereby achieving the purpose of real-time monitoring of the human body's movement status.
[0016] (3) The multifunctional Ag@PDA NPs / AM / SBMA / CNF hydrogel dressing prepared by this invention has a rich three-dimensional network structure. By incorporating Ag@PDA NPs into the network structure of the hydrogel, the Ag@PDA NPs / AM / SBMA / CNF hydrogel has good response sensitivity and reliable physiological motion monitoring capabilities.
[0017] (4) The multifunctional hydrogel dressing prepared by this invention has good adhesion and high adhesion ability in various parts of the human body. It can be adhered to the surface of different parts of the human body (such as finger joints, shoulder joints, knee joints, etc.).
[0018] (5) The multifunctional hydrogel dressing prepared by this invention has excellent antibacterial properties. Ag@PDA NPs themselves have good antibacterial ability. The intrinsic antibacterial properties of the combined hydrogel and the electrostimulation antibacterial strategy, when co-cultured with bacteria for 5 hours, showed that the inhibition diameter first increased and then remained unchanged, and the bactericidal rate against Escherichia coli and Staphylococcus aureus was as high as 100%, demonstrating a long-lasting and effective antibacterial ability.
[0019] (6) The multifunctional hydrogel dressing prepared by this invention has excellent sensing capabilities. Relying on the intrinsic ionic conductivity of SBMA, the ionization conductivity of water in the system, and the ionization enhancement of CNF carboxyl groups, the ionic conductivity and mechanical strength are significantly improved. Combined with Ag@PDANPs, the conductivity is further enhanced and ion shuttle is promoted, giving the material excellent sensing performance. Uniform and regular periodic changes in relative resistance can be generated at different bending angles of the fingers, elbows, eyes, and corners of the mouth, achieving the purpose of stable motion monitoring response.
[0020] (7) The multifunctional hydrogel dressing prepared by this invention can be used as a wound healing dressing, antibacterial dressing, medical adhesive and conductive sensing dressing. Attached Figure Description
[0021] Figure 1 Scanning electron microscopy image of Ag@PDA NPs / AM / SBMA / CNF hydrogel; Detailed Implementation
[0022] These implementation examples are limited to the present invention, but the present invention is not limited to these factual examples.
[0023] Implementation Case 1
[0024] 2 wt% CNF and deionized water were added to a beaker and heated at 25°C to form a CNF solution. An AM:SBMA:CNF solution with a mass ratio of 7:28:10 was then mixed thoroughly to form a transparent solution. Subsequently, 0.5 wt% polyethylene glycol diacrylate and 0.5 wt% 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylphenylacetone were added to the above solution. Finally, 0.5 wt% Ag@PDA NPs (based on the total mass of AM and SBMA) were added to the system, and after a reaction period, an Ag@PDA / AM / SBMA / CNF hydrogel was obtained.
[0025] The results show that the Ag@PDA NPs / AM / SBMA / CNF hydrogel exhibits a continuous and complete three-dimensional network structure. Tensile mechanical tests show a fracture stress of 0.04 MPa and a fracture strain as high as 900%. Adhesion strength tests show a maximum adhesion strength of 0.024 MPa and an adhesion fracture strain of 500%, demonstrating high adhesion and high strength performance. Furthermore, the Ag@PDA NPs / AM / SBMA / CNF hydrogel exhibits a relative change in resistance of up to 30% in response to a single rapid deformation stimulus, with a response time of only 0.33 s and a recovery time of only 0.41 s, demonstrating ultrafast signal feedback. In continuous cyclic testing at different stretching rates, it can stably output a periodic resistance signal with a peak value of 35%~40% at a rate of 10 mm / min and a periodic resistance signal with a peak value of 40%~45% at a rate of 20 mm / min.
[0026] Implementation Case 2
[0027] 2 wt% CNF and deionized water were added to a beaker and heated at 25°C to form a CNF solution. An AM:SBMA:CNF solution with a mass ratio of 7:28:10 was then mixed thoroughly to form a transparent solution. Subsequently, 0.5 wt% polyethylene glycol diacrylate and 0.5 wt% 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylphenylacetone were added to the above solution. Finally, 0.25 wt% Ag@PDA NPs (based on the total mass of AM and SBMA) were added to the system, and after a period of reaction, an Ag@PDA NPs / AM / SBMA / CNF hydrogel was obtained.
[0028] The results show that the Ag@PDA NPs / AM / SBMA / CNF hydrogel exhibits a continuous and complete three-dimensional network structure. Tensile mechanical tests show a fracture stress of 0.02 MPa and a fracture strain as high as 550%. Adhesion strength tests show a maximum adhesion strength of 0.006 MPa and an adhesion fracture strain of 250%, demonstrating high adhesion and high strength performance. Furthermore, the Ag@PDA / AM / SBMA / CNF hydrogel exhibits a relative change in resistance of up to 20% in response to a single rapid deformation stimulus, with a response time of only 0.45 s and a recovery time of only 0.60 s, demonstrating ultrafast signal feedback. In continuous cyclic testing at different stretching rates, it can stably output a periodic resistance signal with a peak value of 20%~30% at a rate of 10 mm / min and a periodic resistance signal with a peak value of 30%~40% at a rate of 20 mm / min.
[0029] Implementation Case 3
[0030] A CNF solution was formed by adding 2 wt% CNF and deionized water to a beaker and incubating at 25°C. An AM:SBMA:CNF solution with a mass ratio of 7:28:10 was then mixed thoroughly to form a transparent solution. Subsequently, 0.5 wt% of polyethylene glycol diacrylate and 0.5 wt% of 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylphenylacetone were added to the above solution. Finally, 0.75 wt% of Ag@PDA NPs (based on the total mass of AM and SBMA) was added to the system, and after a reaction period, an Ag@PDA NPs / AM / SBMA / CNF hydrogel was obtained.
[0031] The results show that the Ag@PDA NPs / AM / SBMA / CNF hydrogel exhibits a continuous and complete three-dimensional network structure. Tensile mechanical tests show a fracture stress of 0.06 MPa and a fracture strain as high as 500%. Adhesion strength tests show a maximum adhesion strength of 0.015 MPa and an adhesion fracture strain of 300%, demonstrating high adhesion and high strength performance. Furthermore, the Ag@PDA / AM / SBMA / CNF hydrogel exhibits a relative change in electrical resistance of up to 25% in response to a single rapid deformation stimulus, with a response time of only 0.50 s and a recovery time of only 0.67 s, demonstrating ultrafast signal feedback. In continuous cyclic testing at different stretching rates, it can stably output a periodic resistance signal with a peak value of 25%~35% at a rate of 10 mm / min and a periodic resistance signal with a peak value of 30%~45% at a rate of 20 mm / min.
[0032] Implementation Case 4
[0033] 2 wt% CNF and deionized water were added to a beaker and heated at 25°C to form a CNF solution. An AM:SBMA:CNF solution with a mass ratio of 7:28:10 was then mixed thoroughly to form a transparent solution. Subsequently, 0.5 wt% polyethylene glycol diacrylate and 2 wt% 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylphenylacetone were added to the above solution, and after a period of reaction, an AM / SBMA / CNF hydrogel was formed.
[0034] The results showed that the AM / SBMA / CNF blank hydrogel exhibited a continuous three-dimensional network structure. Tensile mechanical experiments showed that its fracture stress was 0.01 MPa and its fracture strain was 300%. Adhesion strength experiments showed that the maximum adhesion strength was only 0.001 MPa and the adhesion fracture strain was 120%. Furthermore, the AM / SBMA / CNF hydrogel exhibited a relative change in resistance of up to 15% in response to a single rapid deformation stimulus, with a response time of only 0.63 s and a recovery time of only 0.87 s, demonstrating ultrafast signal feedback. In continuous cyclic testing at different stretching rates, it could stably output a periodic resistance signal with a peak value of 15%~20% at a rate of 10 mm / min and a periodic resistance signal with a peak value of 20%~25% at a rate of 20 mm / min.
[0035] Implementation Case 5
[0036] 2 wt% CNF and deionized water were added to a beaker and heated at 25°C to form a CNF solution. An AM:SBMA:CNF solution with a mass ratio of 7:17:10 was then mixed thoroughly to form a transparent solution. Subsequently, 0.5 wt% polyethylene glycol diacrylate and 2 wt% 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylphenylacetone were added to the above solution, and after a period of reaction, an AM / SBMA / CNF hydrogel was formed.
[0037] The results showed that the AM / SBMA / CNF blank hydrogel exhibited a continuous three-dimensional network structure. Tensile mechanical experiments showed that its fracture stress was 0.007 MPa and its fracture strain was 360%. Adhesion strength experiments showed that the maximum adhesion strength was only 0.0007 MPa and the adhesion fracture strain was 100%.
[0038] Implementation Case 6
[0039] 2 wt% CNF and deionized water were added to a beaker and heated at 25°C to form a CNF solution. An AM:SBMA:CNF solution with a mass ratio of 7:21:10 was then mixed thoroughly to form a transparent solution. Subsequently, 0.5 wt% polyethylene glycol diacrylate and 2 wt% 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylphenylacetone were added to the above solution, and after a period of reaction, an AM / SBMA / CNF hydrogel was formed.
[0040] The results showed that the AM / SBMA / CNF blank hydrogel exhibited a continuous three-dimensional network structure. Tensile mechanical experiments showed that its fracture stress was 0.008 MPa and its fracture strain was 330%. Adhesion strength experiments showed that the maximum adhesion strength was only 0.0008 MPa and the adhesion fracture strain was 110%.
[0041] Implementation Case 7
[0042] 2 wt% CNF and deionized water were added to a beaker and heated at 25°C to form a CNF solution. An AM:SBMA:CNF solution with a mass ratio of 7:28:7 was then mixed thoroughly to form a transparent solution. Subsequently, 0.5 wt% polyethylene glycol diacrylate and 2 wt% 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylphenylacetone were added to the above solution, and after a period of reaction, an AM / SBMA / CNF hydrogel was formed.
[0043] The results showed that the AM / SBMA / CNF blank hydrogel exhibited a continuous three-dimensional network structure. Tensile mechanical experiments showed that its fracture stress was 0.006 MPa and its fracture strain was 340%. Adhesion strength experiments showed that the maximum adhesion strength was only 0.0006 MPa and the adhesion fracture strain was 130%.
[0044] Implementation Case 8
[0045] 2 wt% CNF and deionized water were added to a beaker and heated at 25°C to form a CNF solution. An AM:SBMA:CNF solution with a mass ratio of 7:28:13 was then mixed thoroughly to form a transparent solution. Subsequently, 0.5 wt% polyethylene glycol diacrylate and 2 wt% 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylphenylacetone were added to the above solution, and after a period of reaction, an AM / SBMA / CNF hydrogel was formed.
[0046] The results showed that the AM / SBMA / CNF blank hydrogel exhibited a continuous three-dimensional network structure. Tensile mechanical experiments showed that its fracture stress was 0.014 MPa and its fracture strain was 260%. Adhesion strength experiments showed that the maximum adhesion strength was only 0.0014 MPa and the adhesion fracture strain was 110%.
Claims
1. A method for preparing a self-healing hydrogel with both sensing and antibacterial properties, characterized in that, The method is performed in the following steps: (1) Add a certain mass ratio of dopamine hydrochloride (DA) to a Tris alkaline solution, centrifuge and stir to form a suspension. Add a certain amount of ammonium hydroxide (NH4OH) solution, silver nitrate (AgNO3) solution and deionized water to a beaker, and form a mixed solution of a certain concentration at 25°C. The solution first produces a brown precipitate and then the precipitate disappears. The solution is then completely protected from light. At the same time, add the above suspension to the mixed solution and react for a certain time to form silver@polydopamine nanoparticles (Ag@PDA NPs). (2) Take a certain mass of cellulose nanofibers (CNF) and deionized water and add them to a beaker. At a temperature of 25°C, a CNF solution is formed. Take a certain mass ratio of acrylamide (AM) and 2-(methacryloyloxy)ethyldimethyl-(3-sulfopropyl)ammonium hydroxide (SBMA) monomers and add them to the CNF solution. Mix them evenly to form a transparent solution. (3) Finally, a certain amount of crosslinking agent, an appropriate amount of photoinitiator, and Ag@PDA NPs of different mass ratios were added to the above system using ultraviolet light-initiated self-polymerization technology. After reacting for a period of time, Ag@PDA NPs / AM / SBMA / CNF hydrogel was obtained.
2. The method for preparing a self-healing hydrogel with both sensing and antibacterial functions according to claim 1, characterized in that... In step (1), the mass ratio of Tris base to dopamine hydrochloride (DA) is 1:1 to 5:1, and the reaction time is 20 to 30 hours.
3. The method for preparing a self-healing hydrogel with both sensing and antibacterial functions according to claim 1, characterized in that... The mass concentration of CNF in step (2) is 1~10wt%; the mass ratio of AM:SBMA:CNF is 7:14~34wt%:5~13wt%.
4. The method for preparing a self-healing hydrogel with both sensing and antibacterial functions according to claim 1, characterized in that... In step (3), ultraviolet light-initiated self-polymerization is used to combine a certain amount of crosslinking agent and an appropriate amount of photoinitiator. The crosslinking agent is one or more of polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, ethylene glycol dimethacrylate, etc., and the amount of crosslinking agent is 0.5~2wt% of the monomer mass. The photoinitiator is one or more of 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylphenylacetone, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, etc., and the amount of photoinitiator is 0.5~3wt% of the total monomer mass.
5. The method for preparing a self-healing hydrogel with both sensing and antibacterial functions according to claim 1, characterized in that... In step (3), the mass ratio of Ag@PDA NPs is 0.25~2.0wt% of the total mass of AM and SBMA.
6. A multifunctional hydrogel dressing with sensing and antibacterial properties, exhibiting high adhesion, self-healing, wound-healing promotion, biocompatibility, and the ability to monitor human health and movement, prepared by the method described in any one of claims 1 to 6. The preparation method is simple and easy to operate. A self-healing Ag@PDA NPs / AM / SBMA / CNF hydrogel is obtained by constructing various dynamic reversible interactions, including hydrogen bonds, covalent bonds, non-covalent bonds, and interionic interactions.