Preparation method of moldable composite porous sponge with antibacterial performance

Abstract

The invention discloses a preparation method of a moldable composite porous sponge with antibacterial performance, which comprises the following steps: by taking chitosan as an organic phase, magnesium-doped hydroxyapatite as an inorganic phase and gelatin and glutaraldehyde as cross-linking agents, freeze-drying to obtain the chitosan-magnesium-doped hydroxyapatite composite porous sponge with plasticity and antibacterial effect. The synthesis process is simple, reaction conditions are controllable, batch production is easy, and the prepared chitosan-magnesium-doped hydroxyapatite composite porous sponge has a unique porous structure and has good filling and repairing effects on dentistry and orthopedics.

Description

Technical Field

[0001] The present invention relates to the technical field of biomaterials, and particularly relates to a preparation method of a shapeable composite porous sponge with antibacterial properties. Background Art

[0002] With the increasingly serious aging problem and the diverse development of dietary structures, there are more and more dental problems. If tooth extraction treatment is carried out, dental implantation is required subsequently. If the alveolar ridge in this area is not maintained in a timely manner, continuous absorption and soft tissue reduction will occur, which not only affects subsequent implantation, but also leads to the loss of occlusal chewing function and the unaesthetic appearance of the maxillofacial region. Therefore, it is an urgent problem to be solved to use high-performance bio-scaffold materials for alveolar ridge preservation. Hydroxyapatite (HA) is the main component of human bones and teeth, and synthetic hydroxyapatite is a recognized safe and non-toxic biomaterial. HA has a chemical composition and crystal structure similar to those of bones, is the main inorganic component of bones, has osteoconductivity, and has been widely used in bone filling, medical aesthetics, and oral repair fields. However, when using porous HA powder, the powder state fills the defect area, lacking the hardness, brittleness, and flexibility required for an osteogenic scaffold, and it is difficult to directly transplant and fix in the defect area. Obtaining a shapeable material by compounding with biocompatible organic substances is beneficial for shaping and applying to different defect sites. Among them, chitosan (CS) is a natural polymer basic polysaccharide with biocompatibility and degradability. Compounding with materials such as HA that promote bone proliferation can improve the plasticity of the material and facilitate application.

[0003] Chinese Patent CN 110801538 A discloses a shapeable artificial bone composite material and its preparation method, which is a composition formed by mixing a biodegradable polymer material and inorganic particles distributed in the polymer material. The average molecular weight of the polymer material is 4000Da to 16000Da, the inorganic particles are composed of calcium phosphate compounds, and the artificial bone composite material is in the shape of shapeable plasticine. The present invention provides a shapeable artificial bone composite material and its preparation method that can be freely shaped and freely injected, but organic solvents are used to dissolve the polymer material in the preparation process of the present invention, which has certain toxicity. If not properly handled during the production process, it will not only endanger the health of operators, but also may cause environmental pollution, and the experimental reaction temperature is high, which is not conducive to large-scale industrial production.

[0004] Chinese Patent CN104302267A discloses a dental filling composition containing zirconia powder, with zirconia powder as the core, combined with hydraulic calcium silicate cement, weak acid regulator and volcanic ash components. The fluidity is optimized through particle size control (zirconia ≤ 20μm, cement ≤ 3μm), and the hardening time is precisely regulated by the weak acid regulator, significantly reducing the strong alkalinity of the silicate cement. This material has excellent radiopacity, low microleakage and biocompatibility, and the compressive strength is 2.1 - 6.8MPa, suitable for different clinical needs such as pulp repair and root canal filling, solving the problems of traditional materials relying on heavy metals and strong alkaline irritation. However, the preparation process of this invention has high process requirements, and the component ratio and particle size distribution need to be strictly regulated, otherwise it is easy to affect the hardening time and material homogeneity, which is not conducive to large-scale industrial production.

[0005] Chinese Patent CN117942428A discloses an injectable gel-like bone induction repair material and its preparation method, which is composed of decellularized bone powder and autologous bone collagen, loaded with a high concentration of bone morphogenetic protein (BMP). The preparation process includes deantigenization treatment of bone powder, extraction of collagen by the "acid + enzyme" method, and multi-stage purification of BMP. The obtained material is in a single-phase gel state, and only needs to be rehydrated with normal saline before injection, avoiding clinical temporary modulation. In vitro experiments show that its morphological stability is maintained for more than 7 days, BMP is slowly released for 21 days, and the cell compatibility is excellent. Animal models confirm its significant bone induction ability and better repair effect than traditional materials, solving the three major pain points of existing products, namely complex composition, weak bone induction and inconvenient use. However, the preparation process of this invention has a long preparation period, and the complete process takes 8 - 10 weeks. The extraction cost of natural BMP is high, and the amount of rehydration of the freeze-dried product needs to be accurately controlled. An error of ±5% affects the injection fluidity, and high-concentration BMP may accelerate local blood vessel proliferation.

[0006] Chinese Patent CN108014021A discloses a dental filling and repair material and its preparation method. This material is composed of resin matrix (10 - 20%), additives (0.1 - 0.5%), fillers (55 - 65%) and prepolymerized resin powder (20 - 30%), and the prepolymerized resin powder is polymerized from Bis-GMA. The prepolymerized resin powder is synthesized by the solid-phase method, the resin matrix and photoinitiator / inhibitor are mixed in sequence, nano-silica and glass fillers are added step by step, and finally vacuum mixed with the prepolymerized powder. The obtained material has a flexural strength of 80 - 120MPa and a compressive strength of 200 - 300MPa after curing, and the shrinkage rate is as low as 1.3 - 2%. It has excellent mechanical properties and low polymerization shrinkage characteristics. By optimizing the filler particle size distribution (10nm - 2μm) and multi-stage vacuum stirring process, the problems of high shrinkage rate and insufficient mechanical properties of traditional resins are solved. However, the preparation processes of the raw material nano-silica and prepolymerized powder of this invention are complex, and the cost is higher than that of ordinary glass ion materials. It requires strict support from vacuum mixing equipment, and the cost is expensive, which is not conducive to industrial production requirements. Summary of the Invention

[0007] Aiming at the problems of the existing technology, the present invention aims to provide a method for preparing a composite porous sponge with antibacterial effect and plastic shaping ability by freeze-drying through organic-inorganic blending. While maintaining the integrity of the structure and shape, it takes into account flexibility and plasticity, can well adhere to defect sites of different shapes, is convenient for the repair of actual irregular sites, and meets the requirements of different application scenarios. By regulating the reaction system, a composite porous structure with interconnected pores and antibacterial effect can be obtained.

[0008] In order to achieve the above object, the present invention adopts the following technical solutions:

[0009] A preparation method of a plastic-shaping composite porous sponge with antibacterial performance is specifically implemented according to the following steps:

[0010] Step 1, prepare a gelatin solution: Weigh gelatin in deionized water and stir until completely dissolved to obtain a gelatin solution;

[0011] Step 2, prepare a CS-acetic acid solution: Weigh CS and dissolve it in acetic acid solution, stir until completely dissolved to obtain a CS-acetic acid solution;

[0012] Step 3, prepare a glutaraldehyde solution: Weigh glutaraldehyde in deionized water and stir until completely dissolved to obtain a glutaraldehyde solution;

[0013] Step 4, prepare a Mg-HA solution: Weigh Mg-HA in deionized water and stir until completely dissolved to obtain a Mg-HA solution;

[0014] Step 5, mix the gelatin solution obtained in Step 1 and the CS-acetic acid solution obtained in Step 2, place them in a water bath and stir, and add the CS-acetic acid solution obtained in Step 3 for reaction to obtain a mixed solution;

[0015] Step 6, add the Mg-HA solution obtained in Step 4 to the mixed solution in Step 5 for reaction at room temperature;

[0016] Step 7, pour the solution obtained after the reaction in Step 6 into a silicone mold and freeze it;

[0017] Step 8, freeze-dry the sample frozen in Step 7 at low temperature to obtain a CS / Mg-HA composite porous sponge.

[0018] Further, the temperature of the deionized water in Step 1 is 65°C.

[0019] Further, in Steps 1, 2, 3, and 4, a magnetic stirrer is used during the stirring process, the rotation speed is 500 rpm, and the stirring time is 10 - 120 min.

[0020] Further, the temperature of the water bath in Step 5 is set at 35°C.

[0021] Further, the freezing temperature in Step 7 is -20°C and the freezing duration is 24 h.

[0022] Further, the freeze-drying temperature in Step 8 is -55°C, the vacuum is 40 Pa, and the freeze-drying duration is 24 h.

[0023] Compared with the prior art, the present invention has the following beneficial effects:

[0024] 1. The present invention provides a preparation method of a shapeable composite porous sponge with antibacterial properties. Using CS as the organic phase, Mg-HA as the inorganic phase, and gelatin and glutaraldehyde as crosslinking agents, a CS / Mg-HA composite porous sponge with plasticity, anti-collapse, and antibacterial properties can be obtained only through freeze-drying.

[0025] 2. The CS / Mg-HA composite porous sponge synthesized by the present invention has an interconnected porous structure, good plasticity and antibacterial properties, and can be accurately filled according to different defect sites during the repair process of tooth filling.

[0026] 3. The synthesis method is simple and has good repeatability. The synthesized shape and size are regular, and the stability is good, which is easy for industrial production. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] Figure 1 is the process flow chart of the preparation method of a shapeable composite porous sponge with antibacterial properties of the present invention.

[0028] Figure 2 is the X-ray diffraction pattern of the CS / Mg-HA composite porous sponge prepared in Examples 1-5 of the present invention.

[0029] Figure 3 is the scanning pattern of the CS / Mg-HA composite porous sponge prepared in Examples 1-5 of the present invention.

[0030] Figure 4 is the EDS Mapping pattern of the CS / Mg-HA composite porous sponge prepared in Examples 1-5 of the present invention.

[0031] Figure 5 is the antibacterial pattern of the CS / Mg-HA composite porous sponge prepared in Examples 1-5 of the present invention.

[0032] Figure 6 is the size change pattern after filling of the CS / Mg-HA composite porous sponge prepared in Examples 1-5 of the present invention.

[0033] Figure 7It is the macroscopic view after swelling of the CS / Mg-HA composite porous sponge prepared in Embodiments 1-5 of the present invention. Detailed implementation manners

[0034] The present invention will be further described in detail below with reference to the accompanying drawings and specific implementation manners.

[0035] As Figure 1 shown, the present invention provides a preparation method of a shapeable composite porous sponge with antibacterial properties, which is specifically implemented according to the following steps:

[0036] Step 1, prepare a gelatin solution: Weigh 10% (w / v) gelatin in deionized water at 65°C, stir until completely dissolved. Use a magnetic stirrer during the stirring process, with a rotation speed of 500 rpm and a stirring time of 10 - 120 min to obtain a gelatin solution;

[0037] Step 2, prepare a CS-acetic acid solution: Weigh CS (20 g / L) and dissolve it in a 10 g / L acetic acid solution, stir until completely dissolved. Use a magnetic stirrer during the stirring process, with a rotation speed of 500 rpm and a stirring time of 10 - 120 min to obtain a CS-acetic acid solution;

[0038] Step 3, prepare a glutaraldehyde solution: Weigh 1% (w / v) glutaraldehyde in deionized water, stir until completely dissolved. Use a magnetic stirrer during the stirring process, with a rotation speed of 500 rpm and a stirring time of 10 - 120 min to obtain a glutaraldehyde solution;

[0039] Step 4, prepare a Mg-HA solution: Weigh Mg-HA in deionized water, with a concentration of 2% - 10% (w / v), stir until completely dissolved. Use a magnetic stirrer during the stirring process, with a rotation speed of 500 rpm and a stirring time of 10 - 120 min to obtain a Mg-HA solution;

[0040] Step 5, mix the gelatin solution obtained in Step 1 and the CS-acetic acid solution obtained in Step 2, place them in a water bath and stir. Set the temperature of the water bath to 35°C, and add the CS-acetic acid solution obtained in Step 3 to react to obtain a mixed solution;

[0041] Step 6, add the Mg-HA solution obtained in Step 4 to the mixed solution obtained in Step 5 at room temperature for reaction;

[0042] Step 7, pour the solution obtained after the reaction in Step 6 into a silicone mold and freeze it at -20°C in the refrigerator for 24 h;

[0043] Step 8, freeze-dry the sample after freezing in Step 7 at -55°C and 40 Pa for 24 h to obtain a CS / Mg-HA composite porous sponge.

[0044] Example 1

[0045] Step 1, prepare a gelatin solution: Weigh 5 g of gelatin into 50 mL of deionized water at 65 °C, stir until it becomes yellow and transparent to obtain a gelatin solution. The stirring speed is 500 rpm and the stirring time is 10 min;

[0046] Step 2, prepare a CS-acetic acid solution: Weigh 1 g of CS and add it to 50 mL of acetic acid solution, stir until it is completely dissolved to obtain a CS-acetic acid solution. The stirring speed is 500 rpm and the stirring time is 30 min;

[0047] Step 3, prepare a glutaraldehyde solution: Weigh 0.1 g of glutaraldehyde into 10 mL of deionized water, stir until it is completely dissolved. The stirring speed is 500 rpm and the stirring time is 10 min;

[0048] Step 4, prepare a Mg-HA solution: Weigh 5 g of Mg-HA into 50 mL of deionized water, stir until it is completely dissolved. The stirring speed is 500 rpm and the stirring time is 120 min;

[0049] Step 5, mix the gelatin solution obtained in Step 1 and the CS-acetic acid solution obtained in Step 2, place them in a water bath and stir. The temperature of the water bath is set at 35 °C, and add the CS-acetic acid solution obtained in Step 3 for reaction. The stirring time is 10 min;

[0050] Step 6, add the Mg-HA solution obtained in Step 4 to the mixed solution in Step 5 at room temperature and stir. The stirring time is 4 h;

[0051] Step 7, pour the solution obtained after the reaction in Step 6 into a silicone mold and freeze it in a -20 °C refrigerator for 24 h;

[0052] Step 8, freeze-dry the sample after freezing in Step 7 at -55 °C and 40 Pa for 24 h to obtain a CS:Mg-HA = 1:5 composite porous sponge.

[0053] Example 2

[0054] Step 1, prepare a gelatin solution: Weigh 5 g of gelatin into 50 mL of deionized water at 65 °C, stir until it becomes yellow and transparent to obtain a gelatin solution. The stirring speed is 500 rpm and the stirring time is 10 min;

[0055] Step 2, prepare a CS-acetic acid solution: Weigh 1 g of CS and add it to 50 mL of acetic acid solution, stir until it is completely dissolved to obtain a CS-acetic acid solution. The stirring speed is 500 rpm and the stirring time is 30 min;

[0056] Step 3, prepare glutaraldehyde solution: Weigh 0.1 g of glutaraldehyde and dissolve it in 10 mL of deionized water, stir until completely dissolved, the stirring speed is 500 rpm, and the stirring time is 10 min;

[0057] Step 4, prepare Mg-HA solution: Weigh 4 g of Mg-HA and dissolve it in 50 mL of deionized water, stir until completely dissolved, the stirring speed is 500 rpm, and the stirring time is 120 min;

[0058] Step 5, mix the gelatin solution obtained in Step 1 and the CS-acetic acid solution obtained in Step 2, place them in a water bath and stir, set the temperature to 35 °C, and add the solution in Step 3 for stirring, the stirring time is 10 min;

[0059] Step 6, add the solution obtained in Step 4 to the mixed solution in Step 5 at room temperature and stir, the stirring time is 4 h;

[0060] Step 7, pour the solution obtained after the reaction in Step 6 into a silicone mold and freeze it in a -20 °C refrigerator for 24 h;

[0061] Step 8, freeze-dry the sample after freezing in Step 7 at -55 °C and 40 Pa for 24 h to obtain a CS:Mg-HA = 1:4 composite porous sponge.

[0062] Example 3

[0063] Step 1, prepare gelatin solution: Weigh 5 g of gelatin and dissolve it in 50 mL of deionized water at 65 °C, stir until it becomes yellow and transparent to obtain a gelatin solution, the stirring speed is 500 rpm, and the stirring time is 10 min;

[0064] Step 2, prepare CS-acetic acid solution: Weigh 1 g of CS and add it to 50 mL of acetic acid solution, stir until completely dissolved to obtain a CS-acetic acid solution, the stirring speed is 500 rpm, and the stirring time is 30 min;

[0065] Step 3, prepare glutaraldehyde solution: Weigh 0.1 g of glutaraldehyde and dissolve it in 10 mL of deionized water, stir until completely dissolved, the stirring speed is 500 rpm, and the stirring time is 10 min;

[0066] Step 4, prepare Mg-HA solution: Weigh 3 g of Mg-HA and dissolve it in 50 mL of deionized water, stir until completely dissolved, the stirring speed is 500 rpm, and the stirring time is 120 min;

[0067] Step 5, mix the gelatin solution obtained in Step 1 and the CS-acetic acid solution obtained in Step 2, place them in a water bath and stir, set the temperature to 35 °C, and add the solution in Step 3 for stirring, the stirring time is 10 min;

[0068] Step 6: Add the solution obtained in Step 4 into the mixed solution of Step 5 at room temperature and stir for 4 h.

[0069] Step 7: Pour the solution obtained after the reaction in Step 6 into a silicone mold and freeze it in a refrigerator at -20 °C for 24 h.

[0070] Step 8: Lyophilize the sample frozen in Step 7 at -55 °C and 40 Pa for 24 h to obtain a CS:Mg-HA = 1:3 composite porous sponge.

[0071] Example 4

[0072] Step 1: Prepare a gelatin solution: Weigh 5 g of gelatin into 50 mL of deionized water at 65 °C and stir until it becomes yellow and transparent to obtain a gelatin solution. The stirring speed is 500 rpm and the stirring time is 10 min.

[0073] Step 2: Prepare a CS-acetic acid solution: Weigh 1 g of CS and add it into 50 mL of acetic acid solution, stir until it is completely dissolved to obtain a CS-acetic acid solution. The stirring speed is 500 rpm and the stirring time is 30 min.

[0074] Step 3: Prepare a glutaraldehyde solution: Weigh 0.1 g of glutaraldehyde into 10 mL of deionized water and stir until it is completely dissolved. The stirring speed is 500 rpm and the stirring time is 10 min.

[0075] Step 4: Prepare a Mg-HA solution: Weigh 2 g of Mg-HA into 50 mL of deionized water and stir until it is completely dissolved. The stirring speed is 500 rpm and the stirring time is 120 min.

[0076] Step 5: Mix the gelatin solution obtained in Step 1 and the CS-acetic acid solution obtained in Step 2, place them in a water bath and stir, set the temperature to 35 °C, and add the solution of Step 3 and stir for 10 min.

[0077] Step 6: Add the solution obtained in Step 4 into the mixed solution of Step 5 at room temperature and stir for 4 h.

[0078] Step 7: Pour the solution obtained after the reaction in Step 6 into a silicone mold and freeze it in a refrigerator at -20 °C for 24 h.

[0079] Step 8: Lyophilize the sample frozen in Step 7 at -55 °C and 40 Pa for 24 h to obtain a CS:Mg-HA = 1:2 composite porous sponge.

[0080] Example 5

[0081] Step 1, prepare the gelatin solution: Weigh 5 g of gelatin into 50 mL of deionized water at 65 °C, stir until it becomes yellow and transparent to obtain the gelatin solution. The stirring speed is 500 rpm and the stirring time is 10 min;

[0082] Step 2, prepare the CS-acetic acid solution: Weigh 1 g of CS and add it to 50 mL of acetic acid solution, stir until it is completely dissolved to obtain the CS-acetic acid solution. The stirring speed is 500 rpm and the stirring time is 30 min;

[0083] Step 3, prepare the glutaraldehyde solution: Weigh 0.1 g of glutaraldehyde into 10 mL of deionized water, stir until it is completely dissolved. The stirring speed is 500 rpm and the stirring time is 10 min;

[0084] Step 4, prepare the Mg-HA solution: Weigh 1 g of Mg-HA into 50 mL of deionized water, stir until it is completely dissolved. The stirring speed is 500 rpm and the stirring time is 120 min;

[0085] Step 5, mix the gelatin solution obtained in Step 1 and the CS-acetic acid solution obtained in Step 2, place them in a water bath and stir, set the temperature to 35 °C, and add the solution in Step 3 for stirring. The stirring time is 10 min;

[0086] Step 6, add the solution obtained after the reaction in Step 4 to the mixed solution in Step 5 at room temperature for stirring. The stirring time is 4 h;

[0087] Step 7, pour the solution obtained in Step 6 into a silicone mold and freeze it in a -20 °C refrigerator for 24 h;

[0088] Step 8, freeze-dry the sample after freezing in Step 7 at -55 °C and 40 Pa for 24 h to obtain the CS:Mg-HA = 1:1 composite porous sponge.

[0089] As Figure 2 shown, it is the X-ray diffraction pattern of the CS / Mg-HA composite porous sponge prepared in Examples 1-5 of the present invention. The phase shows that the main product is HA, the black baseline is the XRD spectrum of pure CS, and the CS peak becomes weak with the doping of Mg-HA, indicating that the reaction has been successfully carried out and the preparation of the CS / Mg-HA composite porous sponge has been achieved.

[0090] As Figure 3 shown, it is the scanning electron micrograph of the CS / Mg-HA composite porous sponge prepared in Examples 1-5 of the present invention, Figure 3(a)-(e) are SEM images of the CS:Mg-HA = 1:5, CS:Mg-HA = 1:4, CS:Mg-HA = 1:3, CS:Mg-HA = 1:2, and CS:Mg-HA = 1:1 composite porous sponges at a magnification of 200 times. It can be clearly seen from the figure that the CS / Mg-HA composite sponge has an interconnected porous shape. Figure 3 (f) is the statistical chart of the elemental mass ratio obtained by EDS point. The calcium (magnesium) to phosphorus ratio of the magnesium-doped hydroxyapatite is 1.402.

[0091] As Figure 4 shown, it is the EDS Mapping diagram of the CS / Mg-HA composite porous sponges prepared in Examples 1-5 of the present invention. The elements marked in the upper left corner are calcium, phosphorus, carbon, magnesium, nitrogen, and oxygen in sequence. It can be seen from the figure that the elements are evenly distributed on the matrix, indicating that Mg-HA has been successfully incorporated into the CS-based composite porous sponge.

[0092] As Figure 5 shown, it is the antibacterial diagram of the CS / Mg-HA composite porous sponges prepared in Examples 1-5 of the present invention, proving that the CS / Mg-HA composite porous sponge has antibacterial properties against Staphylococcus aureus. Figure 5 (a)-(e) are the CS:Mg-HA = 1:5, CS:Mg-HA = 1:4, CS:Mg-HA = 1:3, CS:Mg-HA = 1:2, and CS:Mg-HA = 1:1 composite porous sponges respectively. Figure 5 (f) is a schematic diagram of measuring the antibacterial rate of the sample against Staphylococcus aureus by the agar dilution method. Among them, s1-s5 correspond to Examples 1-5 respectively, and the antibacterial rates are 84%, 93%, 98%, 99%, and 99% respectively.

[0093] As Figure 6 shown, it is the size change diagram of the CS / Mg-HA composite porous sponge filled in the present invention. Figure 6 (a) is the original model size of the 3D printed defective tooth. Figure 6 (b), Figure 6 (c) are the model sizes of the Mg-HA / CS composite sponge filling. Figure 6 (a1)-(a3) are the data of the defective part obtained by measuring the model scanned by laser after DLP 3D printing of the defective tooth in Control X. Figure 6 (b1)-(b3) are the data obtained by measuring in Control X after filling the notch with the CS / Mg-HA composite porous sponge prepared in Example 1. Figure 6(c1)-(c3) are the data measured at Control X after the CS / Mg-HA composite porous sponge prepared in Example 5 was filled into the notch. The data before and after the filling of the CS / Mg-HA composite porous sponge highly coincide, proving that the CS / Mg-HA composite porous sponge can be accurately filled according to different defect sites.

[0094] As Figure 7 shown, it is the macroscopic view of the CS / Mg-HA composite porous sponge prepared in Examples 1-5 of the present invention after swelling. Figure 7 (a)-(e) are the macroscopic views of the composite porous sponges of CS:Mg-HA = 1:5, CS:Mg-HA = 1:4, CS:Mg-HA = 1:3, CS:Mg-HA = 1:2, and CS:Mg-HA = 1:1 after swelling, respectively. It can be seen from the figure that after the CS / Mg-HA composite porous sponge was soaked for 2.5 h, the samples remained intact without any disintegration phenomenon.

[0095] Although the specific embodiments of the present invention have been described above, those skilled in the art should understand that this is only for illustration purposes. The protection scope of the present invention is defined by the appended claims. Without departing from the principle and essence of the present invention, those skilled in the art can make various changes or modifications to these embodiments, but these changes and modifications all fall within the protection scope of the present invention.

Claims

1. A preparation method of a shapeable composite porous sponge with antibacterial properties, characterized in that, The implementation is specifically carried out according to the following steps: Step 1, prepare a gelatin solution: Weigh gelatin and dissolve it in deionized water, and stir until it is completely dissolved to obtain a gelatin solution; Step 2, prepare a CS-acetic acid solution: Weigh CS and dissolve it in an acetic acid solution, and stir until it is completely dissolved to obtain a CS-acetic acid solution; Step 3, prepare a glutaraldehyde solution: Weigh glutaraldehyde and dissolve it in deionized water, and stir until it is completely dissolved to obtain a glutaraldehyde solution; Step 4, prepare a Mg-HA solution: Weigh Mg-HA and dissolve it in deionized water, and stir until it is completely dissolved to obtain a Mg-HA solution; Step 5, mix the gelatin solution obtained in Step 1 and the CS-acetic acid solution obtained in Step 2, place them in a water bath and stir, and add the CS-acetic acid solution obtained in Step 3 to react to obtain a mixed solution; Step 6, add the Mg-HA solution obtained in Step 4 to the mixed solution in Step 5 at room temperature to react; Step 7, pour the solution obtained after the reaction in Step 6 into a silicone mold and freeze it; Step 8, freeze-dry the sample after freezing in Step 7 at low temperature to obtain a CS / Mg-HA composite porous sponge.

2. The preparation method of a shapeable composite porous sponge with antibacterial properties according to claim 1, characterized in that, The temperature of the deionized water in Step 1 is 65 °C.

3. The preparation method of a shapeable composite porous sponge with antibacterial properties according to claim 1, characterized in that, In Steps 1, 2, 3, and 4, a magnetic stirrer is used during the stirring process, the rotation speed is 500 rpm, and the stirring time is 10 - 120 min.

4. The preparation method of a shapeable composite porous sponge with antibacterial properties according to claim 1, characterized in that, The temperature set for the water bath in Step 5 is 35 °C.

5. The preparation method of a shapeable composite porous sponge with antibacterial properties according to claim 1, characterized in that, In Step 7, the freezing temperature is -20 °C, and the freezing duration is 24 h.

6. The preparation method of a shapeable composite porous sponge with antibacterial properties according to claim 1, characterized in that, In Step 8, the freeze-drying temperature is -55 °C, the vacuum is 40 Pa, and the freeze-drying duration is 24 h.

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