Hydrogen peroxide response type one-way drainage dressing and preparation method thereof
By preparing hydrogen peroxide-responsive one-way drainage dressing, the problem of exudate management in diabetic foot ulcer wounds is solved, effective management of exudate and detailed understanding of wound conditions is achieved, and wound healing is promoted.
Patent Information
- Application Number
- CN202510396383.7
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-03-31
- Publication Date
- 2025-08-15
AI Technical Summary
Difficulty in the management of diabetic foot ulcer wound exudate. Existing dressings cannot effectively manage exudate, affecting wound healing.
A hydrogen peroxide-responsive unidirectional drainage dressing was prepared, and a zinc oxide film was deposited by preparing a hydrophilic aerogel, and a conductive film was generated by copper ions and HHTP coordination reactions, and a hydrophobic layer was prepared on one side of the conductive film to form a Janus dressing.
Effective management of exudate is achieved, the changes in trace hydrogen peroxide can be monitored, the wound condition can be understood, and wound healing can be promoted.
Smart Images
Figure CN120478702A_ABST
Abstract
Description
Technical Field
[0001] The present invention relates to the technical field of medical materials, and in particular to a hydrogen peroxide-responsive one-way drainage dressing and a preparation method thereof. Background Art
[0002] Diabetic foot ulcers (DFUs) are a major complication of diabetes, and the difficulty of diabetic wound healing has become a major public health challenge. Hyperglycemic tissue exudate, oxidative stress, and neurovascular and vascular lesions are the main factors hindering healing. Diabetic wounds are often accompanied by large amounts of exudate, which provides a breeding ground for bacteria and increases oxidative stress, thereby impairing wound healing.
[0003] In view of the above-mentioned deficiencies, an effective dressing is urgently needed to manage exudate. Summary of the Invention
[0004] The embodiments of the present invention provide a hydrogen peroxide-responsive one-way drainage dressing and a preparation method thereof, which can provide an effective dressing for managing exudate.
[0005] In a first aspect, the present invention provides a method for preparing a hydrogen peroxide-responsive one-way drainage dressing, the method comprising the following steps:
[0006] Step 1, preparing an aerogel with hydrophilic properties;
[0007] Step 2, depositing a zinc oxide thin film on the surface of the aerogel by an ALD process;
[0008] Step 3: Using a liquid phase growth process, copper ions and HHTP are coordinated to react, thereby corroding and occupying the space where the zinc oxide film is located, thereby forming an in-situ conformal conductive film.
[0009] Step 4: Prepare a hydrophobic layer on one side of the aerogel including the conductive film by using an electrospinning process.
[0010] In one possible design, step one includes:
[0011] The pig skin is subjected to decellularization, freeze-drying and pulverization to obtain acellular matrix powder;
[0012] dissolving the decellularized matrix powder to obtain a decellularized matrix solution;
[0013] The acellular matrix solution is freeze-dried and cross-linked to obtain an aerogel.
[0014] In one possible design, step 2 includes:
[0015] A zinc oxide film with a thickness of 40 to 60 nm is deposited on the surface of the aerogel through an ALD process.
[0016] In one possible design, step three includes:
[0017] The aerogel with the zinc oxide film deposited on the surface is immersed in a first solution containing copper ions to perform a first reaction; wherein, in the first reaction, the copper ions react with the zinc oxide film to form an intermediate product;
[0018] After the first reaction is completed, a second solution including HHTP is added to the first solution to carry out a second reaction. After sufficient reaction, a conductive film is obtained in situ conformally at the zinc oxide thin film.
[0019] In a possible design, Cu(OAc)2 is dissolved in the first solution, and the solvent of the first solution and the solvent of the second solution are both methanol.
[0020] In one possible design, both the first reaction and the second reaction are carried out at 60-70°C.
[0021] In one possible design, step 2 includes:
[0022] Placing the aerogel in an ALD reaction chamber and fixing the aerogel using high-temperature glue;
[0023] The temperature was raised to 110-130°C, and a zinc oxide thin film was deposited in an ALD chamber at 110-130°C using diethyl zinc and deionized water as precursors. The deposition process was repeated 280-320 times, and each cycle included: a diethyl zinc pulse of 45-55 ms, a waiting time of 3-6 s, an N2 purge of 18-22 s, a deionized water pulse of 45-55 ms, a waiting time of 3-6 s, and an N2 purge of 18-22 s.
[0024] In one possible design, step 2 includes:
[0025] In the first solution, the concentration of copper ions is 0.16×10 -4 ~0.18×10 -4 mol / ml;
[0026] In the second solution, the concentration of HHTP is 0.0025-0.0030 g / ml.
[0027] In one possible design, step four includes:
[0028] A PCL hydrophobic layer is prepared on one side of the aerogel including the conductive film using an electrospinning process; wherein the electrospinning process parameters include: a spinning solution of 12-13% w / v PCL solution, a 20G electrospinning needle, a voltage of 15-17 kV, a receiving distance of 20-25 cm, a solution flow rate of 0.8-1.2 mL / h, and a spinning time of 1.8-2.2 min.
[0029] In a second aspect, an embodiment of the present invention further provides a hydrogen peroxide-responsive one-way drainage dressing, which is prepared according to any of the above-mentioned preparation methods.
[0030] Compared with the prior art, the present invention has at least the following beneficial effects:
[0031] In this embodiment, a hydrophilic aerogel is first prepared. The aerogel is a porous material with excellent water absorption properties. After obtaining the aerogel, an ALD (atomic layer deposition) process is used to deposit a layer of zinc oxide film on the porous surface of the aerogel. The zinc oxide film serves as a sacrificial layer to be corroded and occupied by copper ions and HHTP, and a conductive film is generated in the space originally occupied by the zinc oxide film. The thickness of the conductive film obtained in this way is basically the same as the thickness of the original zinc oxide film, and it is smooth and uniform, which is conducive to conductivity. A hydrophobic layer is prepared on one side of the conductive film composite aerogel by an electrospinning process, and a one-way drainage Janus dressing is finally obtained. Because the material has good electrical conductivity, it provides a sensing pathway for hydrogen peroxide, enabling the material to monitor changes in trace amounts of hydrogen peroxide, thereby understanding the condition of the wound in more detail. BRIEF DESCRIPTION OF THE DRAWINGS
[0032] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following briefly introduces the drawings required for use in the embodiments or the description of the prior art. Obviously, the drawings described below are some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative work.
[0033] Figure 1 A scanning electron microscope image of the decellularized matrix aerogel provided in an embodiment of the present invention;
[0034] Figure 2 This is an X-ray diffraction image of the dressing provided in an embodiment of the present invention;
[0035] Figure 3 A scanning electron microscope image of a dressing having a conductive film provided in an embodiment of the present invention;
[0036] Figure 4 A scanning electron microscope image of a hydrophobic layer provided in an embodiment of the present invention;
[0037] Figure 5 The wetting effect of different surfaces of the dressing provided by the embodiment of the present invention; Figure 5 a: hydrophilic layer; Figure 5 b: hydrophobic layer;
[0038] Figure 6 The sensing performance of the Janus dressing provided in the embodiment of the present invention to different concentrations of hydrogen peroxide; wherein, Figure 6 a: Gradient response of different concentrations of hydrogen peroxide; Figure 6 b: Response of the dressing as a function of hydrogen peroxide concentration;
[0039] Figure 7 The antibacterial properties of the Janus dressing provided by the embodiment of the present invention;
[0040] Figure 8 The biocompatibility of the Janus dressing provided by the embodiment of the present invention;
[0041] Figure 9 Reaction free energy diagrams comparing powder and film materials provided by the present invention;
[0042] Figure 10 This is a scanning electron microscope image of the hydrophobic layer of a dressing provided in Comparative Example 2 of the present invention. DETAILED DESCRIPTION
[0043] In order to make the purpose, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the drawings in the embodiments of the present invention. Obviously, the described embodiments are part of the embodiments of the present invention, not all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present invention.
[0044] Please refer to Figures 1 to 8 The present invention provides a method for preparing a hydrogen peroxide-responsive one-way drainage dressing, the method comprising the following steps:
[0045] Step 1, preparing an aerogel with hydrophilic properties;
[0046] Step 2, depositing a zinc oxide thin film on the surface of the aerogel by an ALD process;
[0047] Step 3: Using a liquid phase growth process, copper ions and HHTP are coordinated to react, thereby corroding and occupying the space where the zinc oxide film is located, thereby forming an in-situ conformal conductive film.
[0048] Step 4: Prepare a hydrophobic layer on one side of the aerogel including the conductive film by using an electrospinning process.
[0049] In this embodiment, a hydrophilic aerogel is first prepared. The aerogel is a porous material with good water absorption properties. After obtaining the aerogel, an ALD (atomic layer deposition) process is used to deposit a zinc oxide film on the porous surface of the aerogel. The zinc oxide film serves as a sacrificial layer to be reacted with copper ions and HHTP for erosion and occupation, and a conductive film is generated in the space originally occupied by the zinc oxide film. The conductive film obtained in this way is smooth and uniform, which is conducive to conductivity. A hydrophobic layer is prepared on one side of the conductive film composite aerogel by an electrospinning process, and a one-way drainage Janus dressing is finally obtained. Because the material has good electrical conductivity, it provides a sensing pathway for hydrogen peroxide, enabling the material to monitor changes in trace amounts of hydrogen peroxide, thereby understanding the condition of the wound in more detail.
[0050] It should be noted that the reaction pathway of H2O2 on the conductive Cu-HHTP film during the sensing process is as follows: For the Cu-HHTP film, H2O2 molecules first adsorb on the active Cu sites and then dissociate into hydroxyl groups, which also adsorb on the active sites. Subsequently, one of the hydroxyl groups desorbs from the Cu adsorption site, allowing the remaining hydroxyl group to react with H2O2 on the Cu site. The protonated hydrogen atoms generate H2O molecules, which are adsorbed on the active sites. After the H2O molecules desorb, the catalyst matrix returns to its initial state.
[0051] The formation mechanism and process of Cu-HHTP thin films are described below. First, when a zinc oxide film reacts with a solution containing copper ions, a (Zn, Cu) hydroxy complex salt (HDS) is formed. Similar to layered double hydroxides (LDHs), these HDSs consist of layered material sheets, where inorganic / organic interlayer anions connect cations. This structure provides a support framework for subsequent orderly growth by providing a large specific surface area and numerous metal ion sites. Next, the hydroxyl groups on each benzene ring of the HHTP molecules act as ligands, coordinating with the metal ions as the interphase is exposed to the organic linker (HHTP) solution. This coordination reaction is crucial to the orderly growth process as it imparts directionality to the molecular arrangement. The Cu-HHTP structure grows in a specific direction to avoid disordered accumulation. Because HDSs inherently have a layered structure, the Cu-HHTP film also grows layer by layer after interacting with the HHTP linker. Each HHTP molecule, through coordination between its hydroxyl groups and the metal ions, guides the Cu-HHTP molecules to align in a specific pattern, ensuring an orderly structure. As the reaction proceeds, the Cu-HHTP structure becomes more and more ordered, eventually forming a stable MOFs film.
[0052] In this embodiment, the conductive film also has an antibacterial effect. Copper ions can bind to phospholipids or proteins on the bacterial membrane, changing the fluidity and permeability of the membrane. The phenolic hydroxyl group (-OH) in HHTP has a strong polarity and can interact with the phospholipid bilayer of the bacterial membrane through hydrogen bonds or electrostatic interactions.
[0053] In this embodiment, the conductive film is MOFs, which is the abbreviation of Metalorganic Framework. It is a type of crystalline porous material with a periodic network structure formed by the self-assembly of inorganic metal centers (metal ions or metal clusters) and bridging organic ligands. MOFs is an organic-inorganic hybrid material, which is different from both inorganic porous materials and general organic complexes. It has the rigidity of inorganic materials and the flexibility of organic materials. Therefore, HHTP is an essential organic ligand for the synthesis of conductive MOF films.
[0054] In some embodiments of the present invention, step one includes:
[0055] The pig skin is subjected to decellularization, freeze-drying and pulverization to obtain acellular matrix powder;
[0056] dissolving the decellularized matrix powder to obtain a decellularized matrix solution;
[0057] The acellular matrix solution is freeze-dried and cross-linked to obtain an aerogel.
[0058] In this embodiment, the hydrophilic aerogel can be prepared by using a decellularized matrix, and the decellularized matrix has biocompatibility.
[0059] In some embodiments of the present invention, step 2 includes:
[0060] A zinc oxide film having a thickness of 40 to 60 nm (for example, 40 nm, 41 nm, 42 nm, 43 nm, 44 nm, 45 nm, 46 nm, 47 nm, 48 nm, 49 nm, 50 nm, 51 nm, 52 nm, 53 nm, 54 nm, 55 nm, 56 nm, 57 nm, 58 nm, 59 nm or 60 nm) is deposited on the surface of the aerogel by an ALD process.
[0061] In this embodiment, the thickness of the zinc oxide film is optimally within the above range. If the thickness is greater than the above range, the surface roughness will increase. 2+ The (Zn,Cu) hydroxide salt (HDS) layer generated by the reaction is uneven in thickness, which makes the MOFs disordered; it also causes Cu 2+It is difficult for the ZnO layer to fully penetrate the interior, resulting in limited HDS formation and affecting the uniform growth of the MOF. Excessive thickness can also lead to excessive internal stress, causing structural cracking or shedding. Excessive thickness can also increase resistance, affect electron transport, and reduce catalytic or sensing performance. If the thickness is thinner than the above range, the HDS may be incomplete, affecting the growth of the MOF film. Excessive thinness can also lead to a decrease in carrier concentration, affecting electron transport capacity. Excessive thinness can also cause the ZnO layer to dissolve or peel off during the reaction. Excessive thinness can also lead to insufficient reaction in local areas, resulting in an increase in structural defects in the MOF.
[0062] In some embodiments of the present invention, step three includes:
[0063] The aerogel with a zinc oxide film deposited on the surface is immersed in a first solution containing copper ions to perform a first reaction; wherein, in the first reaction, the copper ions replace the zinc in the zinc oxide film;
[0064] After the first reaction is completed, a second solution including HHTP is added to the first solution to carry out a second reaction. After sufficient reaction, a conductive film is obtained in situ conformally at the zinc oxide thin film.
[0065] In this embodiment, the synthesis process of the conductive film is as follows:
[0066] 1.HHTP hydroxyl group and Cu 2+ coordination
[0067] a) The HHTP molecule contains six hydroxyl groups (–OH), three of which are located on each benzene ring. These hydroxyl groups can act as ligands to bind to Cu 2+ Form a stable coordination bond.
[0068] b) This process belongs to metal-organic coordination reaction, that is, the hydroxyl group of HHTP molecule provides electron pair to react with Cu 2+ The Cu–O coordination bonds are formed, thus promoting the ordered assembly of Cu-HHTP structure.
[0069] 2. Intermolecular interactions promote the orderly growth of MOFs
[0070] a) HHTP and Cu 2+ After coordination, Cu-HHTP molecules tend to grow along the layered structure direction of HDS, thus forming ordered layered MOFs.
[0071] b) Since HDS itself is a layered structure, Cu-HHTP will self-assemble along this direction and eventually form an ordered MOFs film structure.
[0072] 3. Intermolecular π-π interaction enhances stability
[0073] a) There is a π-π interaction between the aromatic rings (benzene rings) between HHTP molecules. This force can further promote the close stacking of molecules, making the final Cu-HHTP MOFs structure more stable and ordered.
[0074] In this example, copper (usually a copper salt such as copper acetate) is added first and then HHTP (2,3,6,7,10,11-trihydroxytriphenyl) is added. This is to control the directionality and orderly growth of the coordination reaction, ensuring the formation of a stable and regular MOF structure. Experimental verification shows that if the copper source and HHTP are added together, the following problems will occur:
[0075] 1. Lack of templated growth leads to disordered precipitation. Specifically, Cu 2+ When HHTP is added at the same time, HHTP will quickly react with Cu 2+ Disordered coordination may lead to uneven precipitation and a lack of controllable layered growth process, resulting in disordered stacking between molecules, which will eventually destroy the layered structure of MOFs and reduce the crystallinity and conductivity of the material.
[0076] 2. Affect the uniform distribution of metal ions. Specifically, first introduce Cu 2+ It helps to control its uniform dispersion on the template surface and form HDS with ZnO, thus improving the uniformity of subsequent coordination. 2+ and HHTP were added simultaneously, Cu 2+ There may be local enrichment, resulting in over-coordination in some areas and insufficient coordination in other areas, which ultimately affects the structural uniformity of MOFs.
[0077] In some embodiments of the present invention, Cu(OAc)2 is dissolved in the first solution, and the solvent of the first solution and the solvent of the second solution are both methanol. Of course, other solvents or other copper salts that are soluble in the solvent may also be used.
[0078] In some embodiments of the present invention, the first reaction and the second reaction are both performed at 60-70°C.
[0079] In some embodiments of the present invention, step 2 includes:
[0080] Placing the aerogel in an ALD reaction chamber and fixing the aerogel using high-temperature glue;
[0081] The temperature was raised to 110-130°C, and a zinc oxide thin film was deposited in an ALD chamber at 110-130°C using diethyl zinc and deionized water as precursors. The deposition process was repeated 280-320 times, and each cycle included: a diethyl zinc pulse of 45-55 ms, a waiting time of 3-6 s, an N2 purge of 18-22 s, a deionized water pulse of 45-55 ms, a waiting time of 3-6 s, and an N2 purge of 18-22 s.
[0082] In this embodiment, the above-mentioned ALD process can produce a zinc oxide thin film with a thickness of 40 to 50 nm.
[0083] In some embodiments of the present invention, step 2 includes:
[0084] In the first solution, the concentration of copper ions is 0.16×10 -4 ~0.18×10 -4 mol / ml;
[0085] In the second solution, the concentration of HHTP is 0.0025-0.0030 g / ml.
[0086] In some embodiments of the present invention, step 4 includes:
[0087] A PCL hydrophobic layer is prepared on one side of the aerogel including the conductive film using an electrospinning process; wherein the electrospinning process parameters include: a spinning solution of 12-13% w / v PCL solution, a 20G electrospinning needle, a voltage of 15-17 kV, a receiving distance of 20-25 cm, a solution flow rate of 0.8-1.2 mL / h, and a spinning time of 1.8-2.2 min.
[0088] In this embodiment, the electrospinning process parameters affect the structure of the hydrophobic layer. Among them, the concentration of PCL (polycaprolactone) is particularly important. If the concentration is too high, the spinning will result in a beaded structure.
[0089] An embodiment of the present invention further provides a hydrogen peroxide-responsive one-way drainage dressing, which is prepared according to any of the above-mentioned preparation methods.
[0090] In order to more clearly illustrate the technical solutions and advantages of the present invention, a hydrogen peroxide-responsive one-way drainage dressing and a preparation method thereof are described in detail below through several embodiments.
[0091] Example 1:
[0092] Step 1, preparing an aerogel with hydrophilic properties;
[0093] 1. Take porcine dermal tissue, mince it into small pieces, and stir it in Tris buffer (50mM, pH=8) overnight. After washing with deionized water, stir it in 1% Triton-X100 solution (dissolved in 50mM Tris buffer, pH=8) for 24 hours. After washing with deionized water, stir it in Hanks' balanced salt solution (HBSS) containing 50 units / mL deoxyribonuclease (DNase), 25μg / mL ribonuclease (RNase), and 0.01% trypsin at 37°C for 4 hours. After washing, stir it in 50mM Tris buffer, pH=8 for 12 hours. After washing, freeze-dry and grind to obtain porcine dermal acellular matrix powder.
[0094] 2. Preparation of Porcine Dermal Acellular Matrix Solution
[0095] The porcine dermal acellular matrix powder was stirred in a 1 mg / mL pepsin solution (dissolved in 0.01 M hydrochloric acid) at room temperature for 3 days. After the acellular matrix was dissolved, it was centrifuged at 5000 rpm for 5 minutes to obtain a porcine dermal acellular matrix solution.
[0096] 3. Preparation of Decellularized Matrix Aerogels
[0097] The porcine dermal acellular matrix solution was frozen at -80°C and then dried in a freeze dryer for 72 hours. The sample was then transferred to a glutaraldehyde crosslinking kit containing 25% glutaraldehyde. The freeze-dried sample was placed on a hollow rack within the kit and crosslinked using glutaraldehyde vapor for 24 hours, flipping the sample over once during crosslinking.
[0098] Step 2, depositing a zinc oxide thin film on the surface of the aerogel by an ALD process;
[0099] Preparation of ALD-decellularized matrix aerogels
[0100] The acellular matrix aerogel was placed in the ALD reaction chamber and fixed with high-temperature glue. A zinc oxide film was deposited at 120°C in the ALD chamber using diethylzinc (DEZ) and deionized water as precursors. Parameters included a DEZ pulse (50ms), a wait (5s), an N2 purge (20s), a deionized water pulse (50ms), a wait (5s), and an N2 purge (20s). 300 cycles of this process resulted in a zinc oxide film approximately 50nm thick on the aerogel surface.
[0101] Step 3: Using a liquid phase growth process, copper ions and HHTP erode and occupy the space where the zinc oxide film is located, thereby forming an in-situ conformal conductive film;
[0102] Cu(OAc)2 (0.032 g) was dissolved in 10 mL of methanol to obtain Solution A. The ALD-decellularized matrix aerogel was immersed in Solution A and reacted at 65°C for 12 hours. Subsequently, 2,3,6,7,10,11-hexahydroxytriphenyl (HHTP, 0.028 g) was dissolved in 10 mL of methanol to obtain Solution B, which was then slowly added dropwise to Solution A. The reaction was continued in an oven at 65°C for 24 hours. The resulting product was washed with methanol to remove any residual reactants and dried at 45°C to obtain a conductive film.
[0103] Step 4: preparing a hydrophobic layer on one side of the aerogel including the conductive film by using an electrospinning process;
[0104] A 12% (w / v) PCL solution was prepared using DMF and DCM as solvents. The volume ratio of DMF to DCM was 1:4. The PCL solution was introduced into a 10 mL syringe pump equipped with a 20G electrospinning needle. Subsequently, PCL nanofibers were produced using an electrospinning machine. During this process, a high voltage of 16 kV was applied to the nozzle and receiving platform, with a receiving distance of 22 cm and a solution flow rate of 1 mL / h. Electrospinning took 2 minutes to produce the optimally hydrophobic fiber layer.
[0105] Comparative Example 1
[0106] Comparative Example 1 is substantially the same as Example 1, except that the step 2 of depositing the zinc oxide thin film is not performed, and the conductive film is directly prepared by the liquid phase method.
[0107] The surface of the conductive film obtained in Comparative Example 1 is powdery. Based on the surface morphology of the Cu-HHTP film (obtained in Example 1) and the powdered Cu-HHTP (obtained in Comparative Example 1), the free energy diagram ( Figure 9 ), as can be seen from the figure, the energy barrier for Cu-HHTP powder to activate H2O2 is 0.59 eV, while the reaction energy barrier of the film is reduced to 0.73 eV, indicating that the presence of the Cu-HHTP film helps lower the energy barrier for activating H2O2, making the reaction more likely to occur. For the reaction of catalyzing H2O2 to generate active hydroxyl radicals: H2O2→H2O2*→OH*+OH-, the Cu-HHTP powder releases 2.04 eV, while the Cu-HHTP film releases 2.38 eV, indicating that the Cu-HHTP film is much more capable of catalyzing this reaction than the Cu-HHTP powder. In summary, the continuous, smooth, layered conductive film structure obtained in Example 1 provides a conductive pathway for ion transfer while reducing the activation barrier for H2O2. Therefore, the MOF film is more conducive to H2O2 sensing.
[0108] Comparative Example 2
[0109] Comparative Example 2 is substantially the same as Example 1, except that the concentration of the PCL solution in step 4 is 15% (w / v).
[0110] Please refer to Figure 10 The hydrophobic layer of the product obtained in Comparative Example 2 showed multiple beaded structures.
[0111] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or make equivalent replacements for some of the technical features therein. However, these modifications or replacements do not deviate the essence of the corresponding technical solutions from the spirit and scope of the technical solutions of the various embodiments of the present invention.
Claims
1. A method for preparing a hydrogen peroxide-responsive one-way drainage dressing, characterized in that: The preparation method comprises the following steps: Step 1, preparing an aerogel with hydrophilic properties; Step 2, depositing a zinc oxide thin film on the surface of the aerogel by an ALD process; Step 3: Using a liquid phase growth process, copper ions and HHTP are coordinated to react, thereby corroding and occupying the space where the zinc oxide film is located, thereby forming an in-situ conformal conductive film. Step 4: Prepare a hydrophobic layer on one side of the aerogel including the conductive film by using an electrospinning process.
2. The preparation method according to claim 1, characterized in that The step one comprises: The pig skin is subjected to decellularization, freeze-drying and pulverization to obtain acellular matrix powder; dissolving the decellularized matrix powder to obtain a decellularized matrix solution; The acellular matrix solution is freeze-dried and cross-linked to obtain an aerogel.
3. The preparation method according to claim 1, characterized in that The second step includes: A zinc oxide film with a thickness of 40 to 60 nm is deposited on the surface of the aerogel through an ALD process.
4. The preparation method according to claim 1, characterized in that The step three includes: The aerogel with the zinc oxide film deposited on the surface is immersed in a first solution containing copper ions to perform a first reaction; wherein, in the first reaction, the copper ions react with the zinc oxide film to form an intermediate product; After the first reaction is completed, a second solution including HHTP is added to the first solution to carry out a second reaction. After sufficient reaction, a conductive film is obtained in situ conformally at the zinc oxide thin film.
5. The preparation method according to claim 4, characterized in that Cu(OAc)2 is dissolved in the first solution, and the solvent of the first solution and the solvent of the second solution are both methanol.
6. The preparation method according to claim 4, characterized in that The first reaction and the second reaction are both carried out at 60-70°C.
7. The preparation method according to claim 3, characterized in that The second step includes: Placing the aerogel in an ALD reaction chamber and fixing the aerogel using high-temperature glue; The temperature was raised to 110-130°C, and a zinc oxide thin film was deposited in an ALD chamber at 110-130°C using diethyl zinc and deionized water as precursors. The deposition process was repeated 280-320 times, and each cycle included: a diethyl zinc pulse of 45-55 ms, a waiting time of 3-6 s, an N2 purge of 18-22 s, a deionized water pulse of 45-55 ms, a waiting time of 3-6 s, and an N2 purge of 18-22 s.
8. The preparation method according to claim 4, characterized in that The second step includes: In the first solution, the concentration of copper ions is 0.16×10 -4 ~0.18×10 -4 mol / ml; In the second solution, the concentration of HHTP is 0.0025-0.0030 g / ml.
9. The preparation method according to claim 1, characterized in that The fourth step includes: A PCL hydrophobic layer is prepared on one side of the aerogel including the conductive film using an electrospinning process; wherein the electrospinning process parameters include: a spinning solution of 12-13% w / v PCL solution, a 20G electrospinning needle, a voltage of 15-17 kV, a receiving distance of 20-25 cm, a solution flow rate of 0.8-1.2 mL / h, and a spinning time of 1.8-2.2 min.
10. A hydrogen peroxide-responsive one-way drainage dressing, characterized in that: Prepared according to any one of claims 1 to 9.