Multifunctional composite medical dressing of pH response type porous modified banana core fiber and preparation method of multifunctional composite medical dressing
A pH-responsive multifunctional dressing was prepared by modifying banana core fiber, which solved the problem of insufficient functional integration of medical dressings and achieved high efficiency in antibacterial, hemostatic, water absorption and biocompatibility, thus promoting wound repair.
Patent Information
- Application Number
- CN202511339656.0
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-09-19
- Publication Date
- 2025-12-26
AI Technical Summary
Existing medical dressings lack functional integration, have unstable pH-responsive drug release, and their porous structure makes it difficult to balance leakage prevention and cell migration. Antibacterial components are easily lost, traditional raw materials consume water and space and are difficult to degrade, and waste banana cores have low utilization rates.
Using waste banana core fiber as raw material, a pH-responsive porous modified dressing was prepared through carboxymethylation modification and collagen composite process. Chitosan, baicalin and clindamycin were loaded to form a synergistic system of antibacterial, anti-inflammatory, hemostatic and regenerative effects.
It achieves efficient and broad-spectrum antibacterial properties, rapid hemostasis, ultra-high water absorption, excellent biocompatibility and biodegradability, meeting the needs of multi-stage regulation throughout the entire wound repair cycle.
Smart Images
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Abstract
Description
Technical Field
[0001] This invention relates to the field of medical dressings, specifically to a multifunctional composite medical dressing made of pH-responsive porous modified banana core fiber. Background Technology
[0002] Medical dressings, as core materials for wound repair, need to balance functions such as antibacterial properties, fluid absorption, regeneration promotion, biocompatibility, and intelligent response. However, current technologies face multiple bottlenecks. There is a significant contradiction between the processing and performance of traditional cellulose-based materials (cotton and linen): cotton has high crystallinity, requiring high-temperature, strong alkali dissolution which leads to degradation; linen contains a large amount of lignin, making degumming complex and resulting in poor biocompatibility. Meanwhile, banana core fiber, as a waste resource, possesses advantages such as high cellulose content, low crystallinity, and strong hydroxyl activity, yet it is limited to coarse processing, and its modification potential and resource value remain untapped.
[0003] Existing dressings also suffer from insufficient functional integration. For example, pH-responsive drug release lacks a stable framework, resulting in low release efficiency; porous structures make it difficult to balance leakage prevention and cell migration; and antibacterial and anti-inflammatory components are mostly physically mixed, making them prone to loss. In addition, traditional raw materials consume a lot of water and land, and synthetic dressings are difficult to degrade. Meanwhile, the utilization rate of banana cores, which are discarded annually at a rate exceeding 100 million tons, is less than 5%. Although their degradation rate is suitable for wound healing, they are not being effectively utilized.
[0004] Therefore, developing a composite medical dressing that uses waste banana core fiber as raw material and prepares it through structural design, intelligent response modification and multi-component synergistic strategy, which has the functions of pH-sensitive drug release, porosity, antibacterial and anti-inflammatory properties and high-efficiency repair, has important resource recycling value. Summary of the Invention
[0005] To address the aforementioned problems, this invention provides a pH-responsive porous modified banana core fiber multifunctional composite medical dressing. Using waste banana core fiber as the main raw material, and leveraging its high cellulose content, low crystallinity, and strong hydroxyl activity, the dressing is prepared through innovative dissolution, film-forming, carboxymethylation modification, and collagen composite processes. This dressing achieves highly efficient broad-spectrum antibacterial properties, rapid hemostasis, ultra-high water absorption, excellent biocompatibility and wound healing promotion capabilities, good biodegradability, and environmental friendliness.
[0006] To achieve the above objectives, one technical solution adopted by the present invention is:
[0007] A pH-responsive, porous, modified banana core fiber multifunctional composite medical dressing comprises a porous network of carboxymethylated banana core fibers with an average pore size of 50-200 μm and a porosity of 70%-85%. The dressing is loaded with chitosan, baicalin, and clindamycin, wherein the mass ratio of chitosan to banana core fiber is (0.1-0.3):1, the mass ratio of baicalin to banana core fiber is (0.01-0.09):1, and the mass ratio of clindamycin to banana core fiber is (0.02-0.05):1. The banana core fiber exhibits high cellulose content, low crystallinity, high hydroxyl exposure, and moderate branching.
[0008] This invention also provides a method for preparing a multifunctional composite medical dressing of pH-responsive porous modified banana core fiber, comprising the following steps:
[0009] Step 1: Pretreatment of banana core fiber. Take fresh banana core fiber, remove impurities, add H2O2 solution containing EDTA at a certain mass ratio, stir for pretreatment, wash with water until neutral, vacuum dry at 60±5℃, cut short fibers of 5-10mm, and process with a pulverizer to obtain banana core short fibers (BJCL).
[0010] Step 2: Preparation of composite solution: BJCL, chitosan (CS) with a degree of deacetylation ≥90% and baicalin are mixed in a certain mass ratio and then added to a certain dissolving system. The mixture is stirred at 800-1200 r / min at 25±2℃ until completely dissolved to obtain BJCL / CS / baicalin composite solution.
[0011] Step 3: Porous membrane formation. The composite solution is electrospun to obtain a nanofiber membrane, which is then freeze-dried under vacuum at -50±5℃ for 24 hours to form a porous structure.
[0012] Step 4: Modification and drug loading. The porous membrane is pretreated with 0.5 mol / L NaOH, then carboxymethylated with a 2%–4% chloroacetic acid / NaOH mixture at 30–50 °C for 40–60 min, and then crosslinked with genipin and loaded with a sodium alginate-clindamycin system to obtain the drug-loaded porous membrane.
[0013] Step 5: Dressing Formation. Add 8%–15% fish-derived collagen to the drug-loaded porous membrane, stir to dissolve, and then roll the membrane at a speed of 10–50 mm / s. Follow this with coagulation and drying processes, and finally pass through a Co process. 60 Irradiation sterilization was used to prepare pH-responsive porous dressings.
[0014] In some technical solutions of the present invention, the EDTA mentioned in step 1 is disodium ethylenediaminetetraacetate, the mass ratio of H2O2 solution to EDTA is (10-50):1; the pretreatment temperature is 50-100℃, and the pretreatment time is 30-120min.
[0015] In some technical solutions of the present invention, the mass ratio of chitosan to banana core fiber in step 1 is (0.1-0.3):1; the mass ratio of baicalin to banana core fiber is (0.01-0.09):1.
[0016] In some technical solutions of the present invention, the purity of baicalin in step 2 is ≥98%, and it combines with chitosan through π-π stacking to synergistically enhance antibacterial and anti-inflammatory properties.
[0017] In some technical solutions of the present invention, the dissolution system in step 2 includes an alkali / urea / thiourea / water system, an amine oxide system, and an organic solvent system.
[0018] In some technical solutions of the present invention, the specific preparation process of the alkali / urea / thiourea / water system in step 2 is to dissolve the BJCL / CS / baicalin mixture in LiOH / urea / thiourea / H2O solvent with mass percentages of 5%–10%, 5%–20%, 5%–20%, and 50%–85%, respectively, and then stir and dissolve at room temperature.
[0019] In some technical solutions of the present invention, the specific preparation process of the amine oxide dissolution system in step 2 is to dissolve the BJCL / CS / baicalin mixture in an NMMO solvent with a water content of 3% to 15%, and then stir and dissolve it under vacuum at 80-120°C.
[0020] In some technical solutions of the present invention, the specific preparation process of the organic solvent system in step 2 is to dissolve the BJCL / CS / baicalin mixture in a LiCl / DMAc solvent with a mass fraction of 5% to 12%, and then stir and dissolve it at room temperature.
[0021] In some preferred embodiments of the present invention, the electrospinning process parameters in step 3 include a voltage of 18-22KV and a pushing speed of 1.0-1.5mL / h.
[0022] In some preferred embodiments of the present invention, the temperature range for freeze drying in step 3 is -50°C to 25°C, and the heating rate is 1°C / min, to avoid pore collapse.
[0023] In some technical solutions of the present invention, the mass concentration of the genipin solution in step 4 is 0.5% to 1%, the crosslinking temperature is 30-40℃, and the time is 1 to 2 hours. Genipin forms covalent bonds with the hydroxyl groups of cellulose and the amino groups of chitosan, thereby enhancing the structural stability.
[0024] In some technical solutions of the present invention, the mass ratio of sodium alginate to chitosan in step 4 is 1:(1-9).
[0025] In some technical solutions of the present invention, the solidification and drying process in step 5 involves placing the rolled material in a water solidification bath to remove residual solvent, and then air-drying it at room temperature. The polyester nonwoven material serves as a temporary support substrate and can be peeled off after drying.
[0026] The technical solution of the present invention has the following advantages compared with the prior art:
[0027] 1. This invention discloses a multifunctional composite medical dressing of pH-responsive porous modified banana core fiber. Utilizing the low crystallinity of banana core cellulose and the high proportion of active hydroxyl groups imparted by this low crystallinity, effective dispersion can be achieved in a specific solution system through room temperature stirring. More importantly, the low crystallinity ensures that most hydroxyl groups are in a reactive state. Stepwise carboxymethylation allows for precise control of the hydroxyl substitution degree, significantly improving water absorption and antibacterial activity. This solves the technical pain points of traditional cellulose dissolution processing, which requires high temperatures and complex chemical treatments, as well as low modification efficiency.
[0028] 2. The present invention provides a multifunctional composite medical dressing of pH-responsive porous modified banana core fiber. Taking advantage of the easy solubility and good molecular dispersibility of banana core cellulose, the dressing uses a porous structure that combines electrospun nanofibers with freeze-dried micron-sized pores. The two form a support and transport synergistic network, which overcomes the bottleneck of existing cellulose-based dressings due to their single pore structure or poor connectivity. It also meets the requirements of rapid liquid absorption, cell migration and drug loading.
[0029] 3. This invention provides a multifunctional composite medical dressing made of pH-responsive porous modified banana core fiber. Based on the high hydroxyl exposure of banana core cellulose, its modification effect is effectively enhanced. It forms hydrogen bonds with chitosan and π-π stacking with baicalin. Simultaneously, the high negative charge density after carboxymethylation synergistically constructs a pH-responsive network with sodium alginate, forming a synergistic system of antibacterial, anti-inflammatory, hemostatic, and regenerative effects, achieving multi-stage regulation throughout the entire wound repair cycle. Attached Figure Description
[0030] The technical solution and its beneficial effects of the present invention will become apparent from the following detailed description of specific embodiments in conjunction with the accompanying drawings.
[0031] Figure 1The diagram shows a flowchart of the preparation method of the pH-responsive porous modified banana core fiber multifunctional dressing of the present invention.
[0032] Figure 2 The image shows a comparison of the appearance of the pH-responsive porous modified banana core fiber before (a) and after (b) pretreatment. Detailed Implementation
[0033] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.
[0034] Example 1
[0035] 1. Pretreatment of banana core fiber: Fresh banana core fiber was taken, lignified impurities were removed, and the fiber was chopped. A 30% solution of H2O2 and EDTA was added at a mass ratio of 25:1 (H2O2:EDTA). The mixture was stirred in an 80℃ constant temperature water bath for 90 min at a stirring speed of 600 r / min. To avoid hydroxyl oxidation, 0.1 mol / L NaOH was used to maintain the pH of the system at 7.5-8.0. After washing with water until neutral, the fiber was vacuum dried at 60℃, cut into 8 mm short fibers, and pulverized to obtain banana core short fibers (BJCL).
[0036] 2. Preparation of composite solution: Weigh BJCL, chitosan and baicalin in a mass ratio of 10:2:0.6, mix them and add them to the LiOH / urea / thiourea / H2O system pre-cooled to -12℃ (mass percentages of 8%, 15%, 15% and 62%, respectively). Stir at 1100 r / min for 20 min at 25℃ until completely dissolved.
[0037] 3. Porous membrane formation: After vacuum degassing of the composite solution for 30 min, electrospinning was performed at a voltage of 20 kV and a spinning rate of 1.2 mL / h to obtain a nanofiber membrane. The membrane was then freeze-dried at -50℃ for 24 h at a heating rate of 1℃ / min to form a porous nanofiber membrane.
[0038] 4. Modification and Drug Loading: The porous membrane was pretreated with 0.5 mol / L NaOH solution for 10 min, then transferred to a 3% chloroacetic acid / NaOH mixture (mass ratio 1:1.2) and stirred at 45℃ for 50 min. After crosslinking with 0.8% genipin solution at 35℃ for 1.5 h, it was immersed in a mixture containing 3% sodium alginate and 0.8% clindamycin (sodium alginate: chitosan ratio 1:4) and crosslinked with CaCl2 for 30 min.
[0039] 5. Dressing Formation: Add 12% fish-derived collagen to the drug-loaded porous membrane, stir at 600 rpm for 30 min, roll the membrane at 30 mm / s, remove the solvent in a water coagulation bath, and then air dry. 60 Irradiation sterilization.
[0040] Example 2
[0041] 1. Pretreatment of banana core fiber: Fresh banana core fiber was taken, lignified impurities were removed, and the fiber was chopped. A 30% solution of H2O2 and EDTA was added at a mass ratio of 10:1 (H2O2 to EDTA). The mixture was stirred in a constant temperature water bath at 50℃ for 30 minutes at a stirring speed of 600 r / min. To avoid hydroxyl oxidation, 0.1 mol / L NaOH was used to maintain the pH of the system at 7.5-8.0. After washing with water until neutral, the fiber was vacuum dried at 60℃, cut into 5 mm short fibers, and pulverized to obtain banana core short fibers (BJCL).
[0042] 2. Preparation of composite solution: Weigh BJCL, chitosan and baicalin in a mass ratio of 10:1:0.1, mix them and add them to the LiOH / urea / thiourea / H2O system pre-cooled to -12℃ (mass percentages of 5%, 10%, 15% and 70%, respectively). Stir at 800 r / min for 20 min at 25℃ until completely dissolved.
[0043] 3. Porous membrane formation: After vacuum degassing of the composite solution for 30 min, electrospinning was performed at a voltage of 20 kV and a spinning rate of 1.2 mL / h to obtain a nanofiber membrane. The membrane was then freeze-dried at -50℃ for 24 h at a heating rate of 1℃ / min to form a porous nanofiber membrane.
[0044] 4. Modification and Drug Loading: The porous membrane was pretreated with 0.5 mol / L NaOH solution for 10 min, then transferred to a 2% chloroacetic acid / NaOH mixture (mass ratio 1:1.2) and stirred at 30℃ for 40 min. After crosslinking with 0.5% genipin solution at 30℃ for 1.5 h, it was immersed in a mixture containing 3% sodium alginate and 0.8% clindamycin (sodium alginate: chitosan ratio 1:1) and crosslinked with CaCl2 for 30 min.
[0045] 5. Dressing Formation: Add 8% fish-derived collagen to the drug-loaded porous membrane, stir at 600 rpm for 30 minutes, roll the membrane at 10 mm / s, remove the solvent in a water coagulation bath, and then air dry. 60 Irradiation sterilization.
[0046] Example 3
[0047] 1. Pretreatment of banana core fiber: Fresh banana core fiber was taken, lignified impurities were removed, and the fiber was chopped. A 30% solution of H2O2 and EDTA was added at a mass ratio of 50:1 (H2O2:EDTA). The mixture was stirred in a constant temperature water bath at 100℃ for 120 min at a stirring speed of 600 r / min. To avoid hydroxyl oxidation, 0.1 mol / L NaOH was used to maintain the pH of the system at 7.5-8.0. After washing with water until neutral, the fiber was vacuum dried at 65℃, cut into 10 mm short fibers, and pulverized to obtain banana core short fibers (BJCL).
[0048] 2. Preparation of composite solution: Weigh BJCL, chitosan and baicalin in a mass ratio of 10:3:0.9, mix them and add 8% LiCl / DMAc solvent system, stir at room temperature for 30 min until dissolved;
[0049] 3. Porous membrane formation: After vacuum degassing of the composite solution for 30 min, electrospinning was performed at a voltage of 22 kV and a spinning rate of 1.5 mL / h to obtain a nanofiber membrane. The membrane was then freeze-dried at -55℃ for 24 h at a heating rate of 1℃ / min to form a porous membrane.
[0050] 4. Modification and Drug Loading: The porous membrane was pretreated with 0.5 mol / L NaOH solution for 10 min, then transferred to a 4% chloroacetic acid / NaOH mixture (mass ratio 1:1.2) and stirred at 50℃ for 60 min. After crosslinking with 1% genipin solution at 40℃ for 2 h, it was immersed in a mixture containing 3% sodium alginate and 0.8% clindamycin (sodium alginate:chitosan ratio 1:9) and crosslinked with CaCl2 for 30 min.
[0051] 5. Dressing Formation: Add 15% fish-derived collagen to the drug-loaded porous membrane, stir at 600 rpm for 30 minutes, roll the membrane at 50 mm / s, remove the solvent in a water coagulation bath, and then air dry. 60 Irradiation sterilization.
[0052] Example 4
[0053] 1. Pretreatment of banana core fiber: Fresh banana core fiber was taken, lignified impurities were removed, and the fiber was chopped. A 30% solution of H2O2 and EDTA was added at a mass ratio of 50:1 (H2O2:EDTA). The mixture was stirred in a constant temperature water bath at 100℃ for 120 min at a stirring speed of 600 r / min. To avoid hydroxyl oxidation, 0.1 mol / L NaOH was used to maintain the pH of the system at 7.5-8.0. After washing with water until neutral, the fiber was vacuum dried at 65℃, cut into 10 mm short fibers, and pulverized to obtain banana core short fibers (BJCL).
[0054] 2. Preparation of composite solution: Weigh BJCL, chitosan and baicalin in a mass ratio of 10:3:0.9, mix them and add them to the LiOH / urea / thiourea / H2O system (mass percentages of 8%, 15%, 15% and 62%, respectively) pre-cooled to -12℃. Stir at 1200r / min for 20min at 25℃ until completely dissolved.
[0055] 3. Porous membrane formation: After vacuum degassing of the composite solution for 30 min, electrospinning was performed at a voltage of 22 kV and a spinning rate of 1.5 mL / h to obtain a nanofiber membrane. The membrane was then freeze-dried at -50℃ for 24 h at a heating rate of 1℃ / min to form a porous nanofiber membrane.
[0056] 4. Modification and Drug Loading: The porous membrane was pretreated with 0.5 mol / L NaOH solution for 10 min, then transferred to a 4% chloroacetic acid / NaOH mixture (mass ratio 1:1.2) and stirred at 50℃ for 60 min. After crosslinking with 1% genipin solution at 40℃ for 2 h, it was immersed in a mixture containing 3% sodium alginate and 0.8% clindamycin (sodium alginate: chitosan ratio 1:4) and crosslinked with CaCl2 for 30 min.
[0057] 5. Dressing Formation: Add 15% fish-derived collagen to the drug-loaded porous membrane, stir at 600 rpm for 30 minutes, roll the membrane at 50 mm / s, remove the solvent in a water coagulation bath, and then air dry. 60 Irradiation sterilization.
[0058] Comparative Example 1: Ordinary gauze
[0059] Comparative Example 2: The only difference from Example 1 is that cotton fibers are used.
[0060] Performance testing and characterization:
[0061] Antibacterial performance test: The antibacterial performance of the modified banana core fiber multifunctional dressing obtained in the example was tested according to the antibacterial performance test method of non-leaching antibacterial (inhibitory) products in GB 15979-2002 Hygienic Standard for Disposable Sanitary Products. The bacteria used were Staphylococcus aureus and Escherichia coli.
[0062] Test results explanation:
[0063] 1. Data on the antibacterial activity of the pH-responsive modified banana core fiber multifunctional dressing of this invention against Escherichia coli and Staphylococcus aureus.
[0064]
[0065] 2. Performance test results of the examples and comparative examples
[0066]
[0067] The above description is merely an exemplary embodiment of the present invention and does not limit the scope of patent protection of the present invention. Any equivalent structural or procedural transformations made based on the content of the present invention specification and drawings, or direct or indirect applications in other related technical fields, are similarly included within the scope of patent protection of the present invention.
Claims
1. A pH-responsive, porous, modified banana core fiber multifunctional composite medical dressing, comprising a carboxymethylated modified banana core fiber porous network with an average pore size of 50-200 μm and a porosity of 70%-85%; the dressing is loaded with chitosan, baicalin, and clindamycin, wherein the mass ratio of chitosan to banana core fiber is (0.1-0.3):1, the mass ratio of baicalin to banana core fiber is (0.01-0.09):1, and the mass ratio of clindamycin to banana core fiber is (0.02-0.05):1; the banana core fiber has the characteristics of high cellulose content, low crystallinity, high hydroxyl exposure, and moderate branching.
2. The preparation method of a multifunctional composite medical dressing of pH-responsive porous modified banana core fiber according to claim 1, comprising the following steps: Step 1: Pretreatment of banana core fiber. Take fresh banana core fiber, remove impurities, add H2O2 solution containing EDTA at a certain mass ratio, stir and pretreat at a certain temperature, wash with water until neutral, vacuum dry, cut short fibers, and process with a pulverizer to obtain banana core short fibers (BJCL). Step 2: Preparation of composite solution: BJCL, chitosan (CS), and baicalin are mixed in a certain mass ratio and added to a certain dissolving system. The mixture is stirred until completely dissolved to obtain a BJCL / CS / baicalin composite solution. Step 3: Porous membrane formation. The composite solution is electrospun to obtain a nanofiber membrane, which is then freeze-dried under vacuum to form a porous structure. Step 4: Modification and drug loading. The porous membrane is pretreated with NaOH, then carboxymethylated with a chloroacetic acid / NaOH mixture, and then crosslinked with genipin and loaded with a sodium alginate-clindamycin system to obtain the drug-loaded porous membrane. Step 5: Dressing Formation. Fish-derived collagen is added to the drug-loaded porous membrane, stirred and dissolved, then rolled into a film. Following a coagulation and drying process, it is then coated with a Co... 60 Irradiation sterilization was used to prepare pH-responsive porous dressings.
3. The method for preparing a multifunctional composite medical dressing of pH-responsive porous modified banana core fiber according to claim 2, characterized in that, The EDTA mentioned in step 1 is disodium ethylenediaminetetraacetate, and the mass ratio of H2O2 solution to EDTA is (10-50):1; the pretreatment temperature is 50-100℃; and the pretreatment time is 30-120 min.
4. The method for preparing a multifunctional composite medical dressing of pH-responsive porous modified banana core fiber according to claim 2, characterized in that, The dissolution system described in step 2 includes an alkali / urea / thiourea / water system, an amine oxide system, and an organic solvent system.
5. The method for preparing a multifunctional composite medical dressing of pH-responsive porous modified banana core fiber according to claim 2, characterized in that, The freeze-drying process described in step 3 involves a temperature range of -50°C to 25°C and a heating rate of 1°C / min to prevent pore collapse.
6. The method for preparing a multifunctional composite medical dressing of pH-responsive porous modified banana core fiber according to claim 2, characterized in that, The mass concentration of the genipin solution in step 4 is 0.5% to 1%, and the crosslinking temperature is 30-40℃; the mass ratio of sodium alginate to chitosan is 1:(1-9).
7. The method for preparing a multifunctional composite medical dressing of pH-responsive porous modified banana core fiber according to claim 2, characterized in that, The solidification and drying steps described in step 5 are as follows: the rolled material is placed in a water solidification bath to remove residual solvent, and then air-dried at room temperature. The polyester nonwoven material serves as a temporary support substrate and can be peeled off after drying.