Cellulose-based bioactive filament for wound repair and preparation process of cellulose-based bioactive filament

Abstract

The invention relates to the technical field of medical instruments, and discloses a preparation method of cellulose-based bioactive filaments for wound repair, which comprises the following specific steps: step 1, preparing an alkali / urea / sodium zincate water solvent by using alkali (NaOH, KOH and LiOH), urea, thiourea and ZnO as raw materials, step 2, mixing cellulose and amino acid, and then heating to react for 10-120 minutes at 150-180 DEG C to obtain a reaction product; and 3, directly dissolving the reaction product in the step 2 into the alkali / urea / sodium zincate water solvent prepared in the step 1 at the dissolving temperature of-5 to 5 DEG C, then adding a mixed solution of a polysaccharide raw material, silver nitrate and chloroauric acid into the dissolved solution, standing for 8 to 18 hours at the temperature of 5 to 30 DEG C, and filtering to obtain the product. The cellulose-based chitosan / ZnO bioactive composite filament is prepared by a wet spinning one-step method, so that the antibacterial property, the cytocompatibility and the wound healing promoting effect of a dressing product produced by processes such as weaving subsequently can be greatly improved.

Description

Technical Field

[0001] The present invention relates to the technical field of medical devices, and in particular to a cellulose-based bioactive filament for wound repair and a preparation process thereof. Background Art

[0002] With the frequent occurrence of industrial accidents and environmental degradation, approximately 234.2 million people worldwide require surgical procedures each year. Coupled with the increasing number of chronic ulcers associated with an aging global population, the development of medical dressings has become a hot topic in scientific research. In the late 1970s, degreased cotton gauze, primarily composed of cellulose, began to be widely used in surgical wound care due to its excellent flexibility, biocompatibility, and biodegradability. Currently, cellulose cotton gauze remains the most widely used medical dressing globally, holding over 50% of the market share. However, the structural units of cellulose contain only inert alcoholic hydroxyl groups, resulting in poor bioactivity and creating a bottleneck in the development of cellulose-based biomaterials. The production of environmentally friendly materials from renewable resources has become an international frontier. my country has also included the "research and development of high-value-added renewable resource products" in its "Science and Technology Development Plan." As one of nature's most abundant and readily available biomass resources, the development of new biomedical materials based on cellulose can provide important material support for public health and align with the country's sustainable development strategy.

[0003] Currently, methods for enhancing the bioactivity of cellulose are primarily categorized into chemical modification and physical compounding. Chemical modification primarily involves introducing new functional groups into the cellulose molecular chain or material surface through reactions such as etherification, esterification, graft copolymerization, and oxidation of cellulose hydroxyl groups. For example, researchers have successfully introduced a variety of bioactive groups (carboxymethyl, amide, and quaternary ammonium groups) into cellulose using etherification reactions. Chemical modification can improve cellulose's bioactivity, but the numerous chemical reactions and the involvement of organic reagents can negatively impact the cellulose's physical and chemical properties (such as strength) and biocompatibility. Physical compounding methods can be achieved by directly blending cellulose with active molecules or by in situ polymerization, leveraging the porous structure of regenerated cellulose. For example, the introduction of collagen and hyaluronic acid can effectively improve cell adhesion, while the introduction of polypyrrole can promote specific binding of neural cells to cellulose under electrical stimulation. However, direct compounding methods are often limited by material compatibility, and in situ polymerization carries the risk of residual toxic small molecules such as initiators and crosslinkers. Therefore, finding suitable bioactivated molecules and their simple and green processing methods has become the key to promoting the development of cellulose in the field of biomaterials. Summary of the Invention

[0004] The purpose of the present invention is to provide a cellulose-based bioactive filament for wound repair and a preparation process thereof, which solves the problems raised in the background technology.

[0005] An embodiment of the present application provides a cellulose-based bioactive filament for wound repair, comprising a filament matrix comprising an alkali / urea / sodium zincate aqueous solvent, cellulose, and α-chitosan powder.

[0006] Optionally, the alkali / urea / sodium zincate aqueous solvent is prepared by using alkali (NaOH, KOH, LiOH), urea, thiourea, and ZnO as raw materials, and the content of the alkali / urea / sodium zincate aqueous solvent is less than 2 wt%.

[0007] Optionally, the polysaccharide raw material is prepared by mixing cellulose and α-chitosan powder.

[0008] Optionally, the cellulose content is greater than 50 wt%.

[0009] Optionally, a method for preparing cellulose-based bioactive filaments for wound repair comprises the following specific steps:

[0010] Step 1: Prepare an alkali / urea / sodium zincate aqueous solvent using alkali (NaOH, KOH, LiOH), urea, thiourea, and ZnO as raw materials, select cellulose with a molecular weight of 80,000-120,000 and a-chitosan powder with a deacetylation degree of 60-90%, add them, grind and blend them to prepare a polysaccharide raw material;

[0011] Step 2: mixing cellulose and amino acids, and then heating at 150-180° C. for 10-120 minutes to obtain a reaction product;

[0012] Step 3: directly dissolving the reaction product in step 2 in the alkali / urea / sodium zincate aqueous solvent prepared in step 1 at a dissolution temperature of -5 to 5°C, then adding a mixture of the polysaccharide raw material, silver nitrate and chloroauric acid to the dissolved solution, and standing at 5 to 30°C for 8 to 18 hours;

[0013] Step 4, spinning the solution finally obtained in step 3 on a spinning machine to obtain cellulose-based bioactive filaments for wound repair;

[0014] Step 5, washing the cellulose-based bioactive filament for wound repair prepared in Step 4;

[0015] Step six, drying the cellulose-based bioactive filaments used for wound repair in step five.

[0016] Optionally, the amino acid used in step 2 is one or a combination of methionine, valine, phenylalanine, leucine, tryptophan, and threonine.

[0017] Optionally, the molar ratio of the silver nitrate and chloroauric acid is 10:1-50:1.

[0018] Optionally, the coagulation adopts a multi-stage coagulation bath, the first stage coagulation bath uses an ethylene glycol aqueous solution, the second stage coagulation bath uses a 0.1-1 wt % potassium hydroxide aqueous solution, and the third stage coagulation bath uses a glycerol aqueous solution.

[0019] Compared with the prior art, the technical solution of this application has the following beneficial effects:

[0020] The technical solution of the present application produces cellulose-based chitosan / ZnO bioactive composite filaments by a one-step wet spinning method, which can greatly improve the antibacterial properties, cell compatibility and wound healing promotion of dressing products subsequently produced by weaving and other processes. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] Other features, objects and advantages of the present invention will become more apparent upon reading the detailed description of non-limiting embodiments with reference to the following drawings:

[0022] Figure 1 This is a wet spinning flow chart of a cellulose-based bioactive filament for wound repair and its preparation process according to the present invention;

[0023] Figure 2 This is a technical roadmap for the research and development of a cellulose-based bioactive filament for wound repair and its preparation process. DETAILED DESCRIPTION

[0024] Example 1

[0025] See also Figure 1-2 The present invention provides a technical solution: a cellulose-based bioactive filament for wound repair, comprising a filament matrix, wherein the filament matrix comprises an alkali / urea / sodium zincate aqueous solvent, cellulose and a-chitosan powder.

[0026] In an embodiment of the present application, the alkali / urea / sodium zincate aqueous solvent is prepared by using alkali (NaOH, KOH, LiOH), urea, thiourea, and ZnO as raw materials, and the content of the alkali / urea / sodium zincate aqueous solvent is 2 wt %.

[0027] In an embodiment of the present application, the polysaccharide raw material is prepared by mixing cellulose and α-chitosan powder.

[0028] In an embodiment of the present application, the cellulose content is 50 wt%.

[0029] In an embodiment of the present application, a method for preparing a cellulose-based bioactive filament for wound repair comprises the following specific steps:

[0030] Step 1: Prepare an alkali / urea / sodium zincate aqueous solvent using alkali (NaOH, KOH, LiOH), urea, thiourea, and ZnO as raw materials, select cellulose with a molecular weight of 80,000 and α-chitosan powder with a deacetylation degree of 60%, grind and blend them to prepare a polysaccharide raw material;

[0031] Step 2: mixing cellulose and amino acid, and then heating at 150° C. for 10 minutes to obtain a reaction product;

[0032] Step 3: directly dissolve the reaction product in step 2 in the alkali / urea / sodium zincate aqueous solvent prepared in step 1 at a dissolution temperature of -5°C, then add a mixture of polysaccharide raw material, silver nitrate and chloroauric acid to the dissolved solution, and let it stand at 5°C for 8 hours;

[0033] Step 4, spinning the solution finally obtained in step 3 on a spinning machine to obtain cellulose-based bioactive filaments for wound repair;

[0034] Step 5, washing the cellulose-based bioactive filament for wound repair prepared in Step 4;

[0035] Step six, drying the cellulose-based bioactive filaments used for wound repair in step five.

[0036] In an embodiment of the present application, the type of amino acid used in step 2 is one or a combination of methionine, valine, phenylalanine, leucine, tryptophan, and threonine.

[0037] In an embodiment of the present application, the molar ratio of the added silver nitrate and chloroauric acid is 10:1.

[0038] In an embodiment of the present application, the coagulation adopts a multi-stage coagulation bath, wherein the first stage coagulation bath uses an aqueous solution of ethylene glycol, the second stage coagulation bath uses a 0.1 wt % aqueous solution of potassium hydroxide, and the third stage coagulation bath uses an aqueous solution of glycerol.

[0039] Example 2

[0040] The present invention provides a technical solution: a cellulose-based bioactive filament for wound repair, comprising a filament matrix comprising an alkali / urea / sodium zincate aqueous solvent, cellulose and α-chitosan powder.

[0041] In an embodiment of the present application, the alkali / urea / sodium zincate aqueous solvent is prepared using alkali (NaOH, KOH, LiOH), urea, thiourea, and ZnO as raw materials, and the content of the alkali / urea / sodium zincate aqueous solvent is 1.9 wt %.

[0042] In an embodiment of the present application, the polysaccharide raw material is prepared by mixing cellulose and α-chitosan powder.

[0043] In an embodiment of the present application, the cellulose content is 51 wt%.

[0044] In an embodiment of the present application, a method for preparing a cellulose-based bioactive filament for wound repair comprises the following specific steps:

[0045] Step 1: Prepare an alkali / urea / sodium zincate aqueous solvent using alkali (NaOH, KOH, LiOH), urea, thiourea, and ZnO as raw materials, and add cellulose with a molecular weight of 90,000 and a-chitosan powder with a deacetylation degree of 65% to crush and blend to prepare a polysaccharide raw material;

[0046] Step 2: mixing cellulose and amino acids, and then heating at 160° C. for 30 minutes to obtain a reaction product;

[0047] Step 3: directly dissolve the reaction product in step 2 in the alkali / urea / sodium zincate aqueous solvent prepared in step 1 at a dissolution temperature of -2°C, then add a mixture of polysaccharide raw material, silver nitrate and chloroauric acid to the dissolved solution, and let it stand at 10°C for 10 hours;

[0048] Step 4, spinning the solution finally obtained in step 3 on a spinning machine to obtain cellulose-based bioactive filaments for wound repair;

[0049] Step 5, washing the cellulose-based bioactive filament for wound repair prepared in Step 4;

[0050] Step six, drying the cellulose-based bioactive filaments used for wound repair in step five.

[0051] In an embodiment of the present application, the type of amino acid used in step 2 is one or a combination of methionine, valine, phenylalanine, leucine, tryptophan, and threonine.

[0052] In an embodiment of the present application, the molar ratio of the added silver nitrate and chloroauric acid is 20:1.

[0053] In an embodiment of the present application, the coagulation adopts a multi-stage coagulation bath, wherein the first stage coagulation bath uses an aqueous solution of ethylene glycol, the second stage coagulation bath uses an aqueous solution of 0.25 wt % potassium hydroxide, and the third stage coagulation bath uses an aqueous solution of glycerol.

[0054] Example 3

[0055] The present invention provides a technical solution: a cellulose-based bioactive filament for wound repair, comprising a filament matrix comprising an alkali / urea / sodium zincate aqueous solvent, cellulose and α-chitosan powder.

[0056] In an embodiment of the present application, the alkali / urea / sodium zincate aqueous solvent is prepared using alkali (NaOH, KOH, LiOH), urea, thiourea, and ZnO as raw materials, and the content of the alkali / urea / sodium zincate aqueous solvent is 1.8 wt %.

[0057] In an embodiment of the present application, the polysaccharide raw material is prepared by mixing cellulose and α-chitosan powder.

[0058] In an embodiment of the present application, the cellulose content is 53 wt%.

[0059] In an embodiment of the present application, a method for preparing a cellulose-based bioactive filament for wound repair comprises the following specific steps:

[0060] Step 1: Prepare an alkali / urea / sodium zincate aqueous solvent using alkali (NaOH, KOH, LiOH), urea, thiourea, and ZnO as raw materials, select cellulose with a molecular weight of 100,000 and α-chitosan powder with a deacetylation degree of 75%, grind and blend them to prepare a polysaccharide raw material;

[0061] Step 2: mixing cellulose and amino acids, and then heating at 165° C. for 60 minutes to obtain a reaction product;

[0062] Step 3: directly dissolve the reaction product in step 2 in the alkali / urea / sodium zincate aqueous solvent prepared in step 1 at a dissolution temperature of 0°C, then add a mixture of polysaccharide raw material, silver nitrate and chloroauric acid to the dissolved solution, and let it stand at 15°C for 12 hours;

[0063] Step 4, spinning the solution finally obtained in step 3 on a spinning machine to obtain cellulose-based bioactive filaments for wound repair;

[0064] Step 5, washing the cellulose-based bioactive filament for wound repair prepared in Step 4;

[0065] Step six, drying the cellulose-based bioactive filaments used for wound repair in step five.

[0066] In an embodiment of the present application, the type of amino acid used in step 2 is one or a combination of methionine, valine, phenylalanine, leucine, tryptophan, and threonine.

[0067] In an embodiment of the present application, the molar ratio of the added silver nitrate and chloroauric acid is 30:1.

[0068] In an embodiment of the present application, the coagulation adopts a multi-stage coagulation bath, wherein the first stage coagulation bath uses an aqueous solution of ethylene glycol, the second stage coagulation bath uses a 0.5 wt % aqueous solution of potassium hydroxide, and the third stage coagulation bath uses an aqueous solution of glycerol.

[0069] Example 4

[0070] The present invention provides a technical solution: a cellulose-based bioactive filament for wound repair, comprising a filament matrix comprising an alkali / urea / sodium zincate aqueous solvent, cellulose and α-chitosan powder.

[0071] In an embodiment of the present application, the alkali / urea / sodium zincate aqueous solvent is prepared by using alkali (NaOH, KOH, LiOH), urea, thiourea, and ZnO as raw materials, and the content of the alkali / urea / sodium zincate aqueous solvent is 1.6 wt %.

[0072] In an embodiment of the present application, the polysaccharide raw material is prepared by mixing cellulose and α-chitosan powder.

[0073] In an embodiment of the present application, the cellulose content is 55 wt%.

[0074] In an embodiment of the present application, a method for preparing a cellulose-based bioactive filament for wound repair comprises the following specific steps:

[0075] Step 1: Prepare an alkali / urea / sodium zincate aqueous solvent using alkali (NaOH, KOH, LiOH), urea, thiourea, and ZnO as raw materials, select cellulose with a molecular weight of 100,000 and α-chitosan powder with a deacetylation degree of 80%, grind and blend them to prepare a polysaccharide raw material;

[0076] Step 2: mixing cellulose and amino acids, and then heating at 170° C. for 110 minutes to obtain a reaction product;

[0077] Step 3: directly dissolve the reaction product in step 2 in the alkali / urea / sodium zincate aqueous solvent prepared in step 1 at a dissolution temperature of 2°C, then add a mixture of polysaccharide raw material, silver nitrate and chloroauric acid to the dissolved solution, and let it stand at 20°C for 15 hours;

[0078] Step 4, spinning the solution finally obtained in step 3 on a spinning machine to obtain cellulose-based bioactive filaments for wound repair;

[0079] Step 5, washing the cellulose-based bioactive filament for wound repair prepared in Step 4;

[0080] Step six, drying the cellulose-based bioactive filaments used for wound repair in step five.

[0081] In an embodiment of the present application, the type of amino acid used in step 2 is one or a combination of methionine, valine, phenylalanine, leucine, tryptophan, and threonine.

[0082] In an embodiment of the present application, the molar ratio of the silver nitrate and chloroauric acid added is 10:1-50:1.

[0083] In an embodiment of the present application, the coagulation adopts a multi-stage coagulation bath, wherein the first stage coagulation bath uses an aqueous solution of ethylene glycol, the second stage coagulation bath uses an aqueous solution of 0.75 wt % potassium hydroxide, and the third stage coagulation bath uses an aqueous solution of glycerol.

[0084] With respect to the above embodiments, the present invention measured the silver ion escape rate after 24 hours in each embodiment using atomic absorption spectroscopy, the cell survival rate of the material on mouse fibroblasts (L-929) using the MTT method, and the complete wound repair period detected by the animal full-thickness skin defect model established using SD rats. The specific data are shown in the following table:

[0085]

Claims

1. A cellulose-based bioactive filament for wound repair, comprising a filament matrix, characterized in that: The filament matrix comprises an alkali / urea / sodium zincate aqueous solvent, cellulose and a-chitosan powder.

2. The cellulose-based bioactive filament for wound repair according to claim 1, characterized in that: The alkali / urea / sodium zincate aqueous solvent is prepared by using alkali (NaOH, KOH, LiOH), urea, thiourea and ZnO as raw materials, and the content of the alkali / urea / sodium zincate aqueous solvent is less than 2wt%.

3. The cellulose-based bioactive filament for wound repair according to claim 1, characterized in that: The polysaccharide raw material is prepared by mixing cellulose and a-chitosan powder.

4. The cellulose-based bioactive filament for wound repair according to claim 1, characterized in that: The cellulose content is greater than 50 wt%.

5. The method for preparing a cellulose-based bioactive filament for wound repair according to claim 1, characterized in that: The specific steps are as follows: Step 1, using alkali (NaOH, KOH, LiOH), urea, thiourea, ZnO as raw materials to prepare alkali / urea / sodium zincate aqueous solvent, selecting cellulose with a molecular weight of 80,000-120,000 and a-chitosan powder with a deacetylation degree of 60-90%, and grinding and blending to prepare polysaccharide raw materials; Step 2, mixing cellulose and amino acids, and then heating at 150-180° C. for 10-120 minutes to obtain a reaction product; Step 3, directly dissolving the reaction product in step 2 in the alkali / urea / sodium zincate aqueous solvent prepared in step 1, the dissolution temperature is -5 to 5°C, then adding a mixed solution of polysaccharide raw material, silver nitrate and chloroauric acid to the dissolved solution, and standing at 5 to 30°C for 8 to 18 hours; Step 4, spinning the solution finally obtained in step 3 on a spinning machine to obtain cellulose-based bioactive filaments for wound repair; Step 5, washing the cellulose-based bioactive filaments for wound repair in step 4; Step six, drying the cellulose-based bioactive filaments for wound repair in step five.

6. The cellulose-based bioactive filament for wound repair according to claim 5, characterized in that: The type of amino acid used in step 2 is one or a combination of methionine, valine, phenylalanine, leucine, tryptophan and threonine.

7. The cellulose-based bioactive filament for wound repair according to claim 5, characterized in that: The molar ratio of the silver nitrate and chloroauric acid added is 10:1-50:

1.

8. The cellulose-based bioactive filament for wound repair according to claim 5, characterized in that: The coagulation adopts a multi-stage coagulation bath, wherein the first stage coagulation bath uses an aqueous solution of ethylene glycol, the second stage coagulation bath uses an aqueous solution of 0.1-1 wt % potassium hydroxide, and the third stage coagulation bath uses an aqueous solution of glycerol.

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