Preparation method of silver-based metal-organic framework hydrogel composite and application thereof in antibiosis

Abstract

The application relates to the technical field of functional materials, and discloses a preparation method of a silver-based metal-organic framework hydrogel composite material and application of the silver-based metal-organic framework hydrogel composite material in antibiosis, which comprises the following steps: respectively dissolving silver nitrate and 3-methyl-5-trifluoromethyl-1H-1,2,4-triazole in 5 milliliters of 5% ammonia water according to a molar ratio of 1:1; synthesizing by adopting an interfacial synthesis method, with 5 milliliters of 5% ammonia water as an intermediate layer; avoiding light and standing; adding the silver-based metal-organic framework material into distilled water, and ultrasonic dispersing for a second preset time length; mixing with carbomer with a concentration of 9.8 grams per liter, adding triethanolamine with a concentration of 5 grams per liter when the solution becomes clear; and stirring at a second mixing rate until a uniform gel is formed. The silver-based metal-organic framework hydrogel composite material prepared by the application has excellent antibacterial activity, biocompatibility, appropriate mechanical properties and adhesion, stable rheological properties, and is stronger than a commercial AgNPs-gel.

Description

Technical Field

[0001] This invention relates to the field of functional materials technology, and more specifically, to a method for preparing a silver-based metal-organic framework hydrogel composite material and its application in antibacterial applications. Background Technology

[0002] Antimicrobial resistance has become a major challenge in global public health. Since the advent of penicillin, antibiotics have been widely used in antimicrobial therapy; however, this has also given rise to the persistent problem of antimicrobial resistance. Even with the continuous development and market launch of new antibiotics, bacteria can quickly acquire resistance, making drug-resistant infections one of the leading causes of death in the future. Against this backdrop, developing novel and effective antibiotic-free antimicrobial materials to reduce susceptibility to resistance development has become an urgent research direction. Antimicrobial hydrogels, due to their designable hydrophilic networks and microporous structures, can load and sustain the release of various bactericidal components, making them a major focus of current biomedical research and providing a new approach to solving the problem of antimicrobial resistance.

[0003] Metal-organic frameworks (MOFs) are crystalline materials composed of metal ions or metal clusters linked to organic ligands via coordination bonds, possessing a large specific surface area and abundant active sites. MOFs combine the antibacterial properties of both inorganic and organic materials. Introducing MOFs with abundant active sites into hydrogels allows for the integration of their superior functional characteristics. During the bonding process between MOFs and hydrogels, the functional groups in the hydrogel matrix can complex with the metal ions that construct the MOFs, which helps promote the dispersion of MOFs within the hydrogel. Simultaneously, the slow release of MOFs from the hydrogel reduces their toxicity, successfully overcoming the limitations of traditional MOFs in application and providing broad prospects for the development of novel antibacterial materials.

[0004] However, existing metal-organic framework hydrogel composites still have some shortcomings. First, the crystal structure of some metal-organic framework materials is not well-defined, the synthesis purity is not high, and the stability is poor, affecting their reliability and repeatability in practical applications. Second, the dispersion control of the metal-organic framework in the preparation process of existing composites is insufficient, resulting in non-uniform internal structure of the composites and affecting the stability of their mechanical properties and antibacterial effects. Third, many metal-organic framework hydrogel composites lack good rheological properties, such as shear thinning behavior, self-healing properties, and injectability, which limits their practical application in clinical treatment, especially in scenarios requiring injection administration or dressings for irregular wounds. In addition, the antibacterial activity of existing composites is often not ideal, especially the inhibitory effect on drug-resistant strains such as methicillin-resistant Staphylococcus aureus is limited, the minimum inhibitory concentration is high, and it is difficult to achieve effective antibacterial effects at low doses, which not only increases the cost of use but may also bring higher risks of biotoxicity.

[0005] No effective solutions have yet been proposed to address the problems in the relevant technologies. Summary of the Invention

[0006] In view of the problems in the related technologies, the present invention proposes a method for preparing a silver-based metal-organic framework hydrogel composite material and its application in antibacterial applications, so as to overcome the above-mentioned technical problems existing in the existing related technologies.

[0007] Therefore, the specific technical solution adopted by the present invention is as follows: According to one aspect of the present invention, a method for preparing a silver-based metal-organic framework hydrogel composite material is provided, the method comprising: The preparation of silver-based metal-organic framework materials specifically includes: dissolving silver nitrate and 3-methyl-5-trifluoromethyl-1H-1,2,4-triazole in 5 mL of 5% ammonia water at a molar ratio of 1:1 to obtain a solution; transferring the solution to a test tube for layering to obtain a layered solution; in this layered solution, silver nitrate solution is in the lower layer, ammonia water is in the middle layer, and 3-methyl-5-trifluoromethyl-1H-1,2,4-triazole solution is in the upper layer; allowing the layered solution to stand at room temperature in the dark for a first preset time to obtain the silver-based metal-organic framework material. The preparation of silver-based metal-organic framework hydrogel composite material specifically includes: adding silver-based metal-organic framework material to distilled water, ultrasonically dispersing it under preset ultrasonic conditions for a second preset time to obtain a suspension; mixing the suspension with carbomer 934P at a concentration of 9.8 g / L on a mechanical stirrer at a first mixing rate; when the solution becomes clear, adding triethanolamine at a concentration of 5 g / L to obtain a mixture; stirring the mixture at a second mixing rate until a uniform gel is formed to obtain the silver-based metal-organic framework hydrogel composite material.

[0008] Furthermore, the first preset duration is 4 days, and the second preset duration is 20 seconds; the preset ultrasound conditions are an ultrasound power of 10 kilowatts and a frequency of 60 kilohertz; the first mixing rate is 1000 revolutions per minute, and the second mixing rate is 2000 revolutions per minute.

[0009] Furthermore, the chemical formula of the silver-based metal-organic framework material is [Ag(dmtrz)](Ag-MOF); where dmtrz is deprotonated 3-methyl-5-trifluoromethyl-1H-1,2,4-triazole.

[0010] Furthermore, the crystal structure parameters of the silver-based metal-organic framework material include: space group Iba2 (orthorhombic); cell parameters: a=8.5652(2)Å, b=12.5307(4)Å, c=18.7326(5)Å, α=90°, β=90°, γ=90°; cell volume of 2010.53(10)Å3; and number of asymmetric units within the cell of 4.

[0011] Furthermore, the silver-based metal-organic framework material has a colorless and transparent cubic crystal form.

[0012] Furthermore, the silver-based metal-organic framework hydrogel composite material exhibits a first characteristic absorption peak at 3357 cm⁻¹ and a second characteristic absorption peak at 1602 cm⁻¹ in the Fourier transform infrared spectrum; wherein, the first characteristic absorption peak is generated by nitrogen-hydrogen bond stretching vibration, and the second characteristic absorption peak is generated by carbonyl stretching vibration.

[0013] Furthermore, after freeze-drying, the internal cross-section of the silver-based metal-organic framework hydrogel composite material shows a porous structure, which is used for loading and sustained release of antibacterial components.

[0014] Furthermore, the silver-based metal-organic framework hydrogel composite exhibits a strain of less than 2.314% in the linear viscoelastic region at a fixed frequency of 1 Hz; the silver-based metal-organic framework hydrogel composite exhibits an elastic modulus higher than the viscous modulus at a strain within a deformation range of less than 88.3%, thus providing solid elastic characteristics.

[0015] Furthermore, the elastic modulus of the silver-based metal-organic framework hydrogel composite material is greater than its viscous modulus when subjected to frequency scanning tests at a constant strain of 1.0%; the shear viscosity of the silver-based metal-organic framework hydrogel composite material decreases with increasing frequency, thus providing a shear thinning effect.

[0016] Furthermore, the silver-based metal-organic framework hydrogel composite material has self-healing properties, enabling it to self-repair after breakage; it also has adhesive properties, allowing it to maintain stable adhesion at different bending angles; and it is injectable, allowing it to be extruded through a syringe and formed into the desired shape or pattern.

[0017] According to another aspect of the present invention, an application of a silver-based metal-organic framework hydrogel composite material in the preparation of antibacterial materials is also provided. This application utilizes a method for preparing a silver-based metal-organic framework hydrogel composite material, which, through the release of silver ions from its structure, reduces the toxicity of silver ions while maintaining antibacterial activity, and is used to inhibit the growth of Staphylococcus aureus, Escherichia coli, or methicillin-resistant Staphylococcus aureus.

[0018] The beneficial effects of this invention are as follows: (1) The silver-based metal-organic framework hydrogel composite material prepared by the present invention has excellent antibacterial activity, biocompatibility, appropriate mechanical properties and adhesion, and stable rheology. It is more effective than commercial AgNPs-gel and effectively solves the shortcomings of insufficient antibacterial ability of some medical dressings.

[0019] (2) This invention prepares a silver-based metal-organic framework material with well-defined crystal structure parameters by using a layered static crystallization technique. The crystal form is a colorless and transparent cubic crystal with a specific orthorhombic Iba2 space group structure. The synthesis has high purity and good stability. The silver-based metal-organic framework material is uniformly dispersed in a carbomer hydrogel matrix through optimized ultrasonic dispersion and mechanical stirring processes. The prepared composite material has a highly porous internal structure, which is beneficial for the loading and sustained release of silver ions. The composite material exhibits excellent rheological properties, with viscoelastic behavior similar to that of an elastic solid and obvious shear thinning characteristics under low strain. This gives it good self-healing, adhesion and injectability properties. It can be squeezed out by a syringe without damaging the hydrogel structure and remains stable for a long time after injection. It is particularly suitable for dressings and injection drug delivery systems for irregular wounds.

[0020] (3) The silver-based metal-organic framework hydrogel composite material prepared in this invention exhibits significantly better antibacterial activity than commercial silver nanoparticle gels. Agar plate diffusion experiments confirmed that, at the same concentration, the diameter of the inhibition zone of this composite material against Staphylococcus aureus, Escherichia coli, and methicillin-resistant Staphylococcus aureus was significantly larger than that of commercial silver nanoparticle gels. The minimum inhibitory concentrations determined by bacterial growth curve experiments were 12 μg / mL, 16 μg / mL, and 18 μg / mL, respectively. At the same concentration, commercial silver nanoparticle gels could not effectively inhibit bacterial growth. This composite material achieves slow release of silver ions through the hydrogel matrix, which reduces the biotoxicity of silver ions and maintains long-lasting antibacterial activity. It shows strong inhibitory effects on Gram-positive bacteria, Gram-negative bacteria, and drug-resistant strains, providing a safe and effective new antibiotic-free antibacterial material solution for solving the problem of antibiotic resistance. Attached Figure Description

[0021] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0022] Figure 1 This is a schematic flowchart of a method for preparing a silver-based metal-organic framework hydrogel composite material according to an embodiment of the present invention; Figure 2 This is a crystal diagram of a silver-based metal-organic framework material in a method for preparing a silver-based metal-organic framework hydrogel composite material according to an embodiment of the present invention; Figure 3 This is a diagram of the minimum asymmetric unit of a silver-based metal-organic framework material in a method for preparing a silver-based metal-organic framework hydrogel composite material according to an embodiment of the present invention. Figure 4 This is an X-ray diffraction powder pattern of a silver-based metal-organic framework material in a method for preparing a silver-based metal-organic framework hydrogel composite material according to an embodiment of the present invention. Figure 5 Fourier transform infrared spectra of blank gel and silver-based metal-organic framework hydrogel composite material in a method for preparing a silver-based metal-organic framework hydrogel composite material according to an embodiment of the present invention. Figure 6 This is a diagram illustrating the fabrication of a blank gel, a silver-based metal-organic framework hydrogel composite material, and a commercial silver nanoparticle gel in a method for preparing a silver-based metal-organic framework hydrogel composite material according to an embodiment of the present invention. Figure 7This is a scanning electron microscope image of a blank gel and a silver-based metal-organic framework hydrogel composite material in a method for preparing a silver-based metal-organic framework hydrogel composite material according to an embodiment of the present invention. Figure 8 The figures show the amplitude scanning test diagram, frequency scanning test diagram, and shear rate-viscosity change curve of the silver-based metal-organic framework hydrogel composite material in the preparation method of the silver-based metal-organic framework hydrogel composite material according to an embodiment of the present invention. Figure 9 These are diagrams illustrating the self-healing behavior, dynamic adhesion behavior, and injectability behavior of a silver-based metal-organic framework hydrogel composite material prepared according to an embodiment of the present invention. Figure 10 This is a graph showing the quantitative results of the size and diameter of the inhibition zone of a silver-based metal-organic framework hydrogel composite material against Escherichia coli, Staphylococcus aureus, and methicillin-resistant Staphylococcus aureus in a method for preparing a silver-based metal-organic framework hydrogel composite material according to an embodiment of the present invention. Figure 11 This is a growth curve of Escherichia coli, Staphylococcus aureus, and methicillin-resistant Staphylococcus aureus under the action of different concentrations of silver-based metal-organic framework hydrogel composite material in a preparation method of silver-based metal-organic framework hydrogel composite material according to an embodiment of the present invention. Detailed Implementation

[0023] To further illustrate the various embodiments, the present invention provides accompanying drawings, which are part of the disclosure of the present invention. These drawings are mainly used to illustrate the embodiments and can be used in conjunction with the relevant descriptions in the specification to explain the operating principles of the embodiments. With reference to these drawings, those skilled in the art should be able to understand other possible implementation methods and the advantages of the present invention. The components in the drawings are not drawn to scale, and similar component symbols are generally used to represent similar components.

[0024] According to embodiments of the present invention, a method and system for preparing a silver-based metal-organic framework hydrogel composite material are provided.

[0025] The present invention will now be further described in conjunction with the accompanying drawings and specific embodiments, such as... Figure 1 As shown, according to an embodiment of the present invention, a method for preparing a silver-based metal-organic framework hydrogel composite material is provided, the method comprising: S1. Preparation of silver-based metal-organic framework materials, specifically including: dissolving silver nitrate and 3-methyl-5-trifluoromethyl-1H-1,2,4-triazole in 5 mL of 5% ammonia water at a molar ratio of 1:1 to obtain a solution; transferring the solution to a test tube for layering to obtain a layered solution; in this layered solution, the silver nitrate solution is in the lower layer, the ammonia water is in the middle layer, and the 3-methyl-5-trifluoromethyl-1H-1,2,4-triazole solution is in the upper layer; allowing the layered solution to stand at room temperature in the dark for a first preset time to obtain the silver-based metal-organic framework material; S2. Preparation of silver-based metal-organic framework hydrogel composite material, specifically including: adding silver-based metal-organic framework material to distilled water, ultrasonically dispersing it for a second preset time under preset ultrasonic conditions to obtain a suspension; mixing the suspension with carbomer 934P at a concentration of 9.8 g / L on a mechanical stirrer at a first mixing rate; when the solution becomes clear, adding triethanolamine at a concentration of 5 g / L to obtain a mixture; stirring the mixture at a second mixing rate until a uniform gel is formed to obtain the silver-based metal-organic framework hydrogel composite material.

[0026] In one embodiment, the first preset duration is 4 days, the second preset duration is 20 seconds; the preset ultrasound conditions are an ultrasound power of 10 kW and a frequency of 60 kHz; the first mixing rate is 1000 rpm, and the second mixing rate is 2000 rpm.

[0027] In one embodiment, the chemical formula of the silver-based metal-organic framework material is [Ag(dmtrz)](Ag-MOF); where dmtrz is deprotonated 3-methyl-5-trifluoromethyl-1H-1,2,4-triazole.

[0028] In one embodiment, the crystal structure parameters of the silver-based metal-organic framework material include: space group Iba2 (orthorhombic); cell parameters a=8.5652(2)Å, b=12.5307(4)Å, c=18.7326(5)Å, α=90°, β=90°, γ=90°; cell volume 2010.53(10)Å3; and the number of asymmetric units in the cell is 4.

[0029] In one embodiment, the silver-based metal-organic framework material is a colorless, transparent, cubic crystal.

[0030] In one embodiment, the silver-based metal-organic framework hydrogel composite material exhibits a first characteristic absorption peak at 3357 cm⁻¹ and a second characteristic absorption peak at 1602 cm⁻¹ in the Fourier transform infrared spectrum; wherein the first characteristic absorption peak is generated by nitrogen-hydrogen bond stretching vibration and the second characteristic absorption peak is generated by carbonyl stretching vibration.

[0031] In one embodiment, the silver-based metal-organic framework hydrogel composite material, after freeze-drying, exhibits a porous structure in its internal cross-section, which is used for loading and sustained-release of antibacterial components.

[0032] In one embodiment, the silver-based metal-organic framework hydrogel composite material exhibits a strain of less than 2.314% in the linear viscoelastic region at a fixed frequency of 1 Hz; the silver-based metal-organic framework hydrogel composite material has an elastic modulus higher than its viscous modulus at a strain of less than 88.3% of the deformation range, thus providing solid elastic characteristics.

[0033] In one embodiment, the elastic modulus of the silver-based metal-organic framework hydrogel composite material is greater than its viscous modulus when subjected to frequency scanning tests at a constant strain of 1.0%; the shear viscosity of the silver-based metal-organic framework hydrogel composite material decreases with increasing frequency to provide a shear thinning effect.

[0034] In one embodiment, the silver-based metal-organic framework hydrogel composite material has self-healing properties for autonomous repair after breakage; the silver-based metal-organic framework hydrogel composite material has adhesive properties for maintaining stable adhesion at different bending angles; and the silver-based metal-organic framework hydrogel composite material has injectable properties for extrusion by a syringe to form a desired shape or pattern.

[0035] It should be noted that this invention provides a method for preparing a silver-based metal-organic framework hydrogel composite material. The chemical formula of the silver-based metal-organic framework material is [Ag(dmtrz)](Ag-MOF), where dmtrz is deprotonated 3-methyl-5-trifluoromethyl-1H-1,2,4-triazole. The silver-based metal-organic framework material possesses specific crystal and spatial structures, exhibits high synthetic purity, and good stability. The prepared silver-based metal-organic framework hydrogel composite material is an Ag-MOF carbomer gel (Ag-MOF-gel). Its preparation conditions are mild, the gelation time is moderate, and it possesses viscoelastic behavior and shear-thinning behavior similar to elastic solids. It exhibits good healing, adhesion, and injectability without damaging the hydrogel structure and remains stable for a long period after injection. Agar plate diffusion experiments and bacterial growth curve experiments demonstrated that Ag-MOF-gel has excellent antibacterial activity, which is stronger than that of commercial AgNPs-gel (commercial silver nanoparticle gel). The minimum inhibitory concentrations were 12 µg / mL for Staphylococcus aureus, 16 µg / mL for Escherichia coli, and 18 µg / mL for methicillin-resistant Staphylococcus aureus.

[0036] Specifically, the silver-based metal-organic framework hydrogel composite material prepared by this method has the chemical formula [Ag(dmtrz)](Ag-MOF), such as... Figure 3As shown, dmtrz is deprotonated 3-methyl-5-trifluoromethyl-1H-1,2,4-triazole. The crystal structure parameters of the silver-based metal-organic framework material include: space group Iba2, cell parameters a=8.5652(2)Å, b=12.5307(4)Å, c=18.7326(5)Å, α=90°, β=90°, γ=90°; cell volume is 2010.53(10)Å3, and the number of asymmetric units Z in the cell is 4.

[0037] Specifically, the preparation of silver-based metal-organic framework materials (Ag-MOFs) involves dissolving AgNO3 and 3-methyl-5-trifluoromethyl-1H-1,2,4-triazole (Hdmtrz) in 5 mL of 5% ammonia water at a molar ratio of 1:1. The solutions are then slowly transferred to test tubes, with the AgNO3 solution in the lower layer, the ammonia water in the middle layer, and the Hdmtrz solution in the upper layer. After standing at room temperature in the dark for 4 days, colorless, transparent, cubic crystals are obtained.

[0038] Specifically, such as Figure 2 As shown, the crystal form of silver-based metal-organic framework materials is colorless and transparent cubic crystals.

[0039] Specifically, such as Figure 4 As shown, silver-based metal-organic framework materials have specific crystal and spatial structures, high synthesis purity, and good stability. Their X-ray diffraction powder patterns show clear crystal diffraction peaks.

[0040] Specifically, such as Figure 6 As shown, the preparation of the silver-based metal-organic framework hydrogel composite (Ag-MOF-gel) includes: adding Ag-MOF to high-purity distilled water and ultrasonically dispersing it for 20 s at an ultrasonic power of 10 kW and a frequency of 60 kHz. The suspension is then mixed with 9.8 g / L carbomer 934P on a high-speed mechanical stirrer at a mixing rate of 1000 rpm. When the solution becomes clear, 5 g / L triethanolamine is added, and the mixture is stirred at 2000 rpm until a homogeneous gel is formed. Blank-gel (without gel) serves as a control.

[0041] Specifically, such as Figure 5 As shown, Fourier transform infrared (FT-IR) spectroscopy reveals that Blank-gel and Ag-MOF-gel exhibit the same peak shape, position (3357 cm⁻¹ and 1602 cm⁻¹), and absorption band intensity, which are attributed to NH stretching vibrations and C=O vibrations, indicating no structural changes. The incorporation of Ag-MOF does not lead to structural changes in the carbomer gel.

[0042] Specifically, such as Figure 7As shown, the hydrogel was spread in a petri dish and transferred to a freeze dryer for freeze drying until all water sublimated. The dried sample was then sputter-coated with gold and attached to the sample stage with conductive adhesive. The hydrogel sample was tested by scanning electron microscopy (SEM), and the internal cross-section of the hydrogel showed a highly porous structure.

[0043] Specifically, such as Figure 8 As shown, the present invention also evaluated the rheological properties of Ag-MOF-gel, wherein, Figure 8 (a) shows the results of the amplitude scanning test. Figure 8 (b) shows the results of the frequency scanning experiment. Figure 8 (c) shows the shear rate-viscosity curve. It can be seen that the linear viscoelastic region of Ag-MOF-gel at a fixed frequency of 1 Hz is defined as strain below 2.314%. Within a deformation range of less than 88.3% strain, the elastic modulus (G′) is higher than the viscous modulus (G′′), indicating that Ag-MOF-gel exhibits viscoelastic behavior similar to that of an elastic solid. Figure 8 As shown in (a), frequency sweep tests conducted at a constant strain of 1.0% also revealed the dominant elastic characteristics of Ag-MOF-gel (G′>G′′), as... Figure 8 As shown in (b), the shear viscosity continues to decrease with increasing frequency, and the shear thinning behavior of Ag-MOF-gel is obvious, as shown in (b). Figure 8 As shown in (c).

[0044] Specifically, such as Figure 9 As shown, Figure 9 Image (a) shows the self-healing behavior. Figure 9 (b) shows the dynamic adhesion behavior. Figure 9 Image (c) shows the injectability behavior demonstration; the red image represents the effect after staining with 1% Rhodamine B dye. The healing, adhesion, and injectability of the silver-based metal-organic framework hydrogel composite material prepared in this invention are as follows: without external intervention, the ruptured hydrogel portions can self-heal at the joints, such as... Figure 9 As shown in (a), the hydrogel's adhesion remains excellent when the finger is bent within the range of 0°–180°, as... Figure 9 As shown in (b). Rheological experiments have demonstrated that hydrogels exhibit shear-thinning behavior, thus allowing for easy extrusion via a syringe without clogging or breakage, enabling the acquisition of desired shapes or patterns in a stable gel state, such as... Figure 9 The “GXMU” shown in (c) is shown in the middle.

[0045] Specifically, such as Figure 10As shown, the present invention also tested the antibacterial properties of the prepared silver-based metal-organic framework hydrogel composite material: using Escherichia coli, Staphylococcus aureus, and methicillin-resistant Staphylococcus aureus (MRSA) as targets, the antibacterial effect of Ag-MOF-gel was evaluated using agar plate diffusion experiment and growth curve method. By testing the antibacterial properties of different concentrations of Ag-MOF-gel, its minimum inhibitory concentration was determined.

[0046] Specifically, the agar plate diffusion experiment used in this invention includes: preparing Ag-MOF-gel and AgNPs-gel at a concentration of 1000 µg / mL, respectively, and testing their inhibition zone diameters, with a blank gel as a control group. The inhibition zones of Ag-MOF-gel against S. aureus, E. coli, and MRSA were 1.88±0.20 mm, 1.79±0.14 mm, and 1.85±0.13 mm, respectively, all significantly larger than those of AgNPs-gel (≤0.49±0.14 mm), demonstrating a clear antibacterial advantage.

[0047] Specifically, such as Figure 11 As shown, the minimum inhibitory concentration (MIC) test used in this invention includes: the minimum inhibitory concentrations of Ag-MOF-gel against Staphylococcus aureus, Escherichia coli, and methicillin-resistant Staphylococcus aureus were determined to be 12 µg / mL, 16 µg / mL, and 18 µg / mL, respectively, by growth curve testing and analysis; the same concentration of AgNPs-gel showed exponential growth, indicating that the antibacterial effect of AgNPs-gel is far inferior to that of Ag-MOF-gel.

[0048] According to another embodiment of the present invention, an application of a silver-based metal-organic framework hydrogel composite material in the preparation of antibacterial materials is also provided. The silver-based metal-organic framework hydrogel composite material prepared by a method for preparing a silver-based metal-organic framework hydrogel composite material reduces the toxicity of silver ions and maintains antibacterial activity by releasing silver ions in the structure, and is used to inhibit the growth of Staphylococcus aureus, Escherichia coli or methicillin-resistant Staphylococcus aureus.

[0049] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A method for preparing a silver-based metal-organic framework hydrogel composite material, characterized in that, include: The preparation of silver-based metal-organic framework materials specifically includes: Silver nitrate and 3-methyl-5-trifluoromethyl-1H-1,2,4-triazole were dissolved in 5 mL of 5% ammonia water at a molar ratio of 1:1 to obtain the dissolved solutions. The solution was transferred to a test tube to separate the layers, resulting in a layered solution. In this layered solution, silver nitrate solution was in the lower layer, ammonia water was in the middle layer, and 3-methyl-5-trifluoromethyl-1H-1,2,4-triazole solution was in the upper layer. The layered solution was left to stand at room temperature in the dark for a first preset time to obtain a silver-based metal-organic framework material. The preparation of silver-based metal-organic framework hydrogel composites specifically includes: The silver-based metal-organic framework material was added to distilled water and ultrasonically dispersed under preset ultrasonic conditions for a second preset time to obtain a suspension. The suspension was mixed with carbomer 934P at a concentration of 9.8 g / L on a mechanical stirrer at a first mixing rate. When the solution became clear, triethanolamine at a concentration of 5 g / L was added to obtain a mixture. The mixture was stirred at a second mixing rate until a uniform gel was formed, thus obtaining a silver-based metal-organic framework hydrogel composite material.

2. The method for preparing a silver-based metal-organic framework hydrogel composite material according to claim 1, characterized in that, The first preset duration is 4 days, and the second preset duration is 20 seconds; The preset ultrasonic conditions are an ultrasonic power of 10 kilowatts and a frequency of 60 kilohertz. The first mixing rate is 1000 revolutions per minute, and the second mixing rate is 2000 revolutions per minute.

3. The method for preparing a silver-based metal-organic framework hydrogel composite material according to claim 1, characterized in that, The chemical formula of the silver-based metal-organic framework material is [Ag(dmtrz)](Ag-MOF); where dmtrz is deprotonated 3-methyl-5-trifluoromethyl-1H-1,2,4-triazole.

4. The method for preparing a silver-based metal-organic framework hydrogel composite material according to claim 3, characterized in that, The crystal structure parameters of the silver-based metal-organic framework material include: The space group is orthorhombic Iba2; The unit cell parameters are: a=8.5652(2)Å, b=12.5307(4)Å, c=18.7326(5)Å, α=90°, β=90°, γ=90°; The cell volume is 2010.53(10)Å3; the number of asymmetric units in the cell is 4.

5. The method for preparing a silver-based metal-organic framework hydrogel composite material according to claim 4, characterized in that, The silver-based metal-organic framework material has a colorless, transparent, cubic crystal form.

6. The method for preparing a silver-based metal-organic framework hydrogel composite material according to claim 1, characterized in that, The silver-based metal-organic framework hydrogel composite material exhibits a first characteristic absorption peak at 3357 cm⁻¹ and a second characteristic absorption peak at 1602 cm⁻¹ in the Fourier transform infrared spectrum; wherein the first characteristic absorption peak is generated by nitrogen-hydrogen bond stretching vibration and the second characteristic absorption peak is generated by carbonyl stretching vibration.

7. The method for preparing a silver-based metal-organic framework hydrogel composite material according to claim 6, characterized in that, After freeze-drying, the silver-based metal-organic framework hydrogel composite material exhibits a porous structure in its internal cross-section, which is used for loading and slow-release of antibacterial components.

8. The method for preparing a silver-based metal-organic framework hydrogel composite material according to claim 6, characterized in that, The strain of the silver-based metal-organic framework hydrogel composite material in the linear viscoelastic region at a fixed frequency of 1 Hz is less than 2.314%. The silver-based metal-organic framework hydrogel composite material has an elastic modulus higher than its viscous modulus at strains with a deformation range of less than 88.3%, and is used to provide solid elastic characteristics.

9. The method for preparing a silver-based metal-organic framework hydrogel composite material according to claim 6, characterized in that, The silver-based metal-organic framework hydrogel composite material exhibits a greater elastic modulus than its viscous modulus during frequency scanning tests at a constant strain of 1.0%. The shear viscosity of the silver-based metal-organic framework hydrogel composite material decreases with increasing frequency, thus providing a shear thinning effect.

10. The application of a silver-based metal-organic framework hydrogel composite material in the preparation of antibacterial materials, wherein the silver-based metal-organic framework hydrogel composite material is prepared by the preparation method of any one of claims 1-9, characterized in that, The silver-based metal-organic framework hydrogel composite material reduces the toxicity of silver ions and maintains antibacterial activity by releasing silver ions from the structure, and is used to inhibit the growth of Staphylococcus aureus, Escherichia coli or methicillin-resistant Staphylococcus aureus.

Images