High-strength, high-biocompatibility fungal fiber and methods of making and using same
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- WUHAN TEXTILE UNIV
- Filing Date
- 2026-06-22
- Publication Date
- 2026-08-07
AI Technical Summary
[0004]目前国内外已针对菌物纤维的制备与应用开展相关研究,但现有技术仍存在诸多难以克服的技术缺陷,核心表现为无法同时实现菌物纤维制品高强度与高生物相容性的兼顾
(1)本申请中,菌物原材料的主要成分是几丁质高分子,经过碱处理后,一方面,高浓度 OH-可破坏几丁质分子间的强氢键网络,打破结晶屏障,使反应试剂充分渗透至分子链内部;另一方面,OH-作为强亲核试剂,催化乙酰氨基的酰胺键发生碱性水解,使乙酰基以乙酸盐的形式脱离糖环,完成几丁质高分子的脱乙酰化。
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Figure CN122522453A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of bio-based functional fiber preparation technology, specifically to a high-strength, highly biocompatible fungal fiber, its preparation method, and its application. Background Technology
[0002] With the continued advancement of the global "dual carbon" strategy, the demand for biodegradable and highly biosafe materials is rapidly increasing in fields such as biomedicine, green textiles, and environmentally friendly packaging. Traditional petrochemical-based synthetic fibers have inherent defects such as non-degradability, poor biocompatibility, and high pollution and energy consumption in the production process. Natural plant fibers such as cotton and linen face problems such as long planting cycles, large land resource occupation, and low upper limits of mechanical properties, making it difficult to meet the stringent requirements of high-end application scenarios.
[0003] Fungal fiber is a novel bio-based fiber prepared from fungal mycelium. Its core component is a natural covalent cross-linked complex formed by chitin and β-glucan. It naturally possesses complete biodegradability, excellent biocompatibility, and low immunogenicity. Furthermore, it can be prepared through fermentation of agricultural and forestry organic waste, with a short production cycle and low carbon footprint, and has broad application prospects in multiple fields.
[0004] Currently, research has been conducted both domestically and internationally on the preparation and application of fungal fibers. However, existing technologies still suffer from numerous insurmountable technical defects, the core of which is the inability to simultaneously achieve both high strength and high biocompatibility in fungal fiber products. Chemical modification processes used to improve mechanical strength severely damage the natural ordered structure of fibers, leaving behind toxic and harmful reagents, significantly reducing the biocompatibility and biosafety of the materials. While mild physical treatment processes can preserve biocompatibility, they cannot effectively solve the problems of poor fiber dispersibility, weak inter-fiber bonding, and insufficient mechanical strength of the products. At the same time, existing technologies also suffer from low raw material utilization, lengthy preparation processes, high production costs, poor product performance stability and batch consistency, rapid degradation of mechanical properties in humid environments, and the inability to achieve precise performance control for different application scenarios. These shortcomings severely limit the large-scale promotion and high-end application of fungal fiber products. Summary of the Invention
[0005] This application provides a high-strength, highly biocompatible fungal fiber, its preparation method, and its application. The preparation method first obtains a fungal polymer material with a deacetylation rate of 70% to 100% by controlling the time and temperature of alkali treatment. Then, the fungal polymer material is uniformly dissolved in a dispersant solution (a mixed solvent composed of an ionic liquid and a co-solvent N,N-dimethylformamide) to obtain a fungal polymer solution with a mass fraction of 0.5% to 40%. Continuous and uniform fungal filament fibers with excellent biocompatibility, a diameter of 10 to 500 μm, and a breaking strength ≥100 MPa are obtained by wet spinning.
[0006] The fungal filament fibers prepared in this application can be used in fields such as apparel textiles, medical textiles, and industrial textiles.
[0007] In a first aspect, embodiments of this application provide a method for preparing high-strength, highly biocompatible fungal fibers, comprising the following steps: S1, the crushed fungal raw materials are mixed with an alkaline solution and heated in a water bath to remove soluble polysaccharides and glycoproteins from the fungal raw materials. Then, after cooling to room temperature, they are centrifuged and precipitated. The precipitate is freeze-dried to obtain fungal polymer materials with a deacetylation rate of 70%~99%. S2, the fungal polymer material obtained in step S1 is fully dissolved in the dispersant at a temperature of 50℃~160℃ and a rotation speed of 500rpm~3000rpm to obtain a fungal polymer solution with a mass fraction of 0.5%~40%. The dispersant is a mixed solvent composed of an ionic liquid and a co-solvent N,N-dimethylformamide; The ionic liquid is one or more of the following: 1-hexyl-3-methylimidazolium chloride, 1-octyl-3-methylimidazolium bromide, 1-butyl-2,3-dimethylimidazolium tetrafluoroborate, 1-methoxyethyl-3-methylimidazolium acetate, 1-hydroxyethyl-3-methylimidazolium chloride, 1-butyl-3-methylimidazolium chloride, 1-allyl-3-methylimidazolium chloride, 1-ethyl-3-methylimidazolium acetate, 1-butyl-3-methylimidazolium acetate, 1-allyl-3-methylimidazolium acetate, 1-(2-hydroxyethyl)-3-methylimidazolium acetate, 1-aminoethyl-3-methylimidazolium acetate, and 1-methoxyethyl-3-methylimidazolium acetate. S3, the fungal polymer solution obtained in step S2 is extruded from the spinneret by a metering pump into the coagulation bath for solidification and stretching. The initially formed fungal fiber filaments are then repeatedly introduced into the displacement bath for solvent displacement and further stretching. The displaced fungal fiber filaments are heat-set to remove moisture, dried and wound to obtain continuous and uniform fungal filament fibers with excellent biocompatibility, a diameter of 10~500μm and a breaking strength ≥100MPa.
[0008] Furthermore, in step S1, the deacetylation rate of the fungal polymer material is obtained by adjusting the heating time and temperature of the water bath.
[0009] Furthermore, in step S1, the alkaline solution is one or more of lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium carbonate, and sodium bicarbonate, and the molar concentration of the alkaline solution is 5~13 mol / L.
[0010] Furthermore, the water bath heating time is 30 minutes to 4 hours, and the temperature is 60℃ to 100℃.
[0011] Furthermore, in the dispersant, the mass fraction of N,N-dimethylformamide is 10% to 60%.
[0012] Furthermore, the fungal raw material is a processing byproduct of medicinal fungi, and the medicinal fungi are Ganoderma lucidum, Trametes versicolor, Poria cocos, Polyporus umbellatus, Inonotus obliquus, or Lycoperdon perlatum.
[0013] Furthermore, in step S3, the coagulation bath is one or more of deionized water, ethyl acetate, alcohols, acetone, alkaline solutions, and metal salt solutions; the coagulation bath temperature is 80℃~100℃; the coagulation bath time is 15min~2h; and the coagulation stretching ratio is 10%~300%.
[0014] Furthermore, in step S3, the displacement bath is one or more of deionized water, alcohol, alkaline solution, and metal salt solution; the temperature of the displacement bath is 80℃~100℃; the displacement stretching ratio is 10%~300%; the displacement bath time is 5min~2h; and the number of displacements is 2~7.
[0015] Secondly, embodiments of this application provide a high-strength, highly biocompatible microbial fiber, which is prepared by any of the aforementioned technical solutions.
[0016] By combining and twisting these high-strength, highly biocompatible fungal fibers, and by parallel aggregation and directional twisting of the fungal fibers, fungal yarns with a diameter of 20μm~5mm can be obtained, which have a uniform structure, complete morphology, and stable performance.
[0017] This fungal yarn can be used in fields such as apparel textiles, medical textiles, and industrial textiles.
[0018] Compared with the prior art, the present invention has the following beneficial effects: (1) In this application, the main component of the fungal raw material is chitin polymer. After alkali treatment, on the one hand, the high concentration of OH- can destroy the strong hydrogen bond network between chitin molecules, break the crystal barrier, and allow the reaction reagent to fully penetrate into the molecular chain; on the other hand, OH-, as a strong nucleophile, catalyzes the alkaline hydrolysis of the amide bond of acetaminophen, so that the acetyl group leaves the sugar ring in the form of acetate, and completes the deacetylation of chitin polymer.
[0019] This application obtains a fungal polymer material with a deacetylation rate of 70%~100% by controlling the time and temperature of alkali treatment (water bath heating). Then, the fungal polymer material is uniformly dissolved in a dispersant solution (a mixed solvent composed of ionic liquid and co-solvent N,N-dimethylformamide) to obtain a fungal polymer solution with a mass fraction of 0.5%~40%. Continuous and uniform fungal filament fibers with excellent biocompatibility, a diameter of 10~500μm, and a breaking strength ≥100MPa are obtained by wet spinning.
[0020] (2) In this application, a mixed solvent consisting of an ionic liquid and a co-solvent, N,N-dimethylformamide, is used as the dispersant. First, the ionic liquid comes into contact with the fungal polymer, opening the hydrogen bonds between the polymer chains. The anions and cations of the ionic liquid can break the inherent strong hydrogen bond network between and within chitin molecules. The anions of the ionic liquid itself form a new hydrogen bond network with the fungal polymer, breaking the tight entanglement of the polymer chains and forming a new hydrogen bond network with the polar sites on the chitin chains, thus achieving full solubilization of the polymer. The co-solvent can directly and synergistically solubilize the chitin by forming hydrogen bonds, while reducing the viscosity of the system and improving the diffusion efficiency of the ionic liquid, further optimizing the dissolution effect and system homogeneity. Furthermore, DMF molecules are highly polar and have low steric hindrance. Their carbonyl groups can form strong hydrogen bonds with the hydroxyl and amino groups of fungal polysaccharides, efficiently destroying the original hydrogen bond network, allowing the molecular chains to fully extend and degrade less. Moreover, DMF is easy to remove, and after molding, the polysaccharide chains can rebuild dense hydrogen bonds, resulting in a uniform fiber structure with few defects. Therefore, the fungal fibers produced have excellent mechanical strength.
[0021] (3) In this application, the processing by-products of medicinal fungi are used as raw materials, which not only solves the problem of environmentally friendly waste disposal, but also obtains high-quality raw materials with lower crystallinity and easier solubility. This reduces the difficulty of the process from the source and realizes the green preparation of low-value waste into high-value bio-based fibers, which is economical, environmentally friendly and industrially feasible.
[0022] (4) The high-strength, highly biocompatible microbial fiber obtained in this application can be applied to fields such as apparel textiles, medical textiles and industrial textiles.
[0023] The above description is only an overview of the technical solution of this application. In order to better understand the technical means of this application and to implement it in accordance with the contents of the specification, and to make the above and other objects, features and advantages of this application more obvious and understandable, the following are specific embodiments of this application. Attached Figure Description
[0024] To more clearly illustrate the technical solutions of this application, the accompanying drawings used in this application will be briefly described below. Obviously, the drawings described below are merely some embodiments of this application. For those skilled in the art, other drawings can be obtained from these drawings without any creative effort.
[0025] Figure 1 This is a photograph of the Ganoderma lucidum mycelium polymer solution in Example 1.
[0026] Figure 2 This is a microscopic morphology diagram of the high-strength, highly biocompatible fungal fibers prepared in Example 1.
[0027] Figure 3 The stress-strain curves of the high-strength, highly biocompatible fungal fibers prepared in Example 1 are shown.
[0028] Figure 4 The stress-strain curve of the fungal fiber prepared in Comparative Example 1 is shown.
[0029] Figure 5 The stress-strain curve of the fungal fiber prepared in Comparative Example 2 is shown.
[0030] Figure 6 The stress-strain curve of the fungal fibers prepared in Comparative Example 3 is shown.
[0031] Figure 7 The stress-strain curve of the fungal fiber prepared in Comparative Example 4 is shown.
[0032] Figure 8 The results show the cell compatibility evaluation of the fungal fibers prepared in Example 1 and Comparative Examples 1-4. Detailed Implementation
[0033] The embodiments of the technical solution of this application will now be described in detail with reference to the accompanying drawings. These embodiments are only used to more clearly illustrate the technical solution of this application and are therefore merely examples, and should not be used to limit the scope of protection of this application.
[0034] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application pertains; the terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the application; the terms “comprising” and “having”, and any variations thereof, in the specification, claims, and foregoing description of the drawings are intended to cover non-exclusive inclusion.
[0035] In the description of the embodiments of this application, technical terms such as "first" and "second" are used only to distinguish different objects and should not be construed as indicating or implying relative importance or implicitly specifying the number, specific order, or primary and secondary relationship of the indicated technical features. In the description of the embodiments of this application, "multiple" means two or more, unless otherwise explicitly defined.
[0036] In this document, the term "embodiment" means that a particular feature, structure, or characteristic described in connection with an embodiment may be included in at least one embodiment of this application. The appearance of this phrase in various places throughout the specification does not necessarily refer to the same embodiment, nor is it a separate or alternative embodiment mutually exclusive with other embodiments. It will be explicitly and implicitly understood by those skilled in the art that the embodiments described herein can be combined with other embodiments.
[0037] In the description of the embodiments in this application, the term "and / or" is merely a description of the relationship between related objects, indicating that three relationships can exist. For example, A and / or B can represent: A existing alone, A and B existing simultaneously, and B existing alone. Additionally, the character " / " in this document generally indicates that the preceding and following related objects have an "or" relationship.
[0038] In the description of the embodiments of this application, the term "multiple" refers to two or more (including two), similarly, "multiple sets" refers to two or more (including two sets), and "multiple pieces" refers to two or more (including two pieces).
[0039] In the description of the embodiments of this application, unless otherwise expressly specified and limited, technical terms such as "installation," "connection," "joining," and "fixing" should be interpreted broadly. For example, they can refer to a fixed connection, a detachable connection, or an integral part; they can refer to a mechanical connection or an electrical connection; they can refer to a direct connection or an indirect connection through an intermediate medium; they can refer to the internal communication of two components or the interaction between two components. For those skilled in the art, the specific meaning of the above terms in the embodiments of this application can be understood according to the specific circumstances.
[0040] This application provides a method for preparing high-strength, highly biocompatible fungal fibers, comprising the following steps: S1. The crushed fungal raw material is mixed with an alkaline solution and heated in a water bath to remove soluble polysaccharides and glycoproteins from the fungal raw material. Then, after cooling to room temperature, it is centrifuged and precipitated. The precipitate is freeze-dried to obtain fungal polymer materials with a deacetylation rate of 70%~99%.
[0041] Among them, the fungal raw materials are processing by-products of medicinal fungi, such as Ganoderma lucidum, Trametes versicolor, Poria cocos, Polyporus umbellatus, Inonotus obliquus, or Lycoperdon perlatum.
[0042] The alkaline solution is one or more of lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium carbonate, and sodium bicarbonate, and the molar concentration of the alkaline solution is 5~13 mol / L (20wt%~50wt%).
[0043] The water bath heating time is 30 minutes to 4 hours, and the temperature is 60℃ to 100℃.
[0044] In step S1, the deacetylation rate of the microbial polymer material obtained by adjusting the heating time and temperature of the water bath is 70%~99%.
[0045] Alkali concentration, reaction time, and reaction temperature all affect deacetylation: the deacetylation reaction begins at an alkali concentration of 5 mol / L (20 wt%), and the deacetylation rate increases rapidly with increasing alkali concentration. The reaction rate and deacetylation conversion rate reach their peak at 13 mol / L (50 wt%). When the concentration exceeds 13 mol / L, the deacetylation reaction is significantly inhibited at 15 mol / L (60 wt%). Regarding reaction time, 0–90 min is the rapid reaction range, during which the deacetylation rate can rapidly increase to 70%–80%. After 90 min, the reaction enters a slow phase, with the deacetylation rate slowly increasing to over 90% and gradually stabilizing. Increasing the temperature in the 70–100 ℃ range only slightly promotes the deacetylation reaction and slightly increases the deacetylation rate, with limited overall regulatory effect, and is not the core controlling factor of the deacetylation process.
[0046] S2, the fungal polymer material obtained in step S1 is fully dissolved in the dispersant at a temperature of 50℃~160℃ and a rotation speed of 500rpm~3000rpm to obtain a fungal polymer solution with a mass fraction of 0.5%~40%. The dispersant is a mixed solvent composed of an ionic liquid and a co-solvent, N,N-dimethylformamide.
[0047] The mass fraction of N,N-dimethylformamide in the dispersant is 10% to 60%.
[0048] As the mass fraction of N,N-dimethylformamide increases, the solubility of the mixed solvent in fungal fibers first increases and then decreases, reaching its peak when the mass fraction of N,N-dimethylformamide is around 20%.
[0049] If the mass fraction of N,N-dimethylformamide exceeds 60% and the ionic liquid content is too low, the dissolution effect on the fungal raw materials will be significantly reduced.
[0050] The ionic liquid is one or more of the following: 1-hexyl-3-methylimidazolium chloride, 1-octyl-3-methylimidazolium bromide, 1-butyl-2,3-dimethylimidazolium tetrafluoroborate, 1-methoxyethyl-3-methylimidazolium acetate, 1-hydroxyethyl-3-methylimidazolium chloride, 1-butyl-3-methylimidazolium chloride, 1-allyl-3-methylimidazolium chloride, 1-ethyl-3-methylimidazolium acetate, 1-butyl-3-methylimidazolium acetate, 1-allyl-3-methylimidazolium acetate, 1-(2-hydroxyethyl)-3-methylimidazolium acetate, 1-aminoethyl-3-methylimidazolium acetate, and 1-methoxyethyl-3-methylimidazolium acetate.
[0051] S3, the fungal polymer solution obtained in step S2 is extruded from the spinneret by a metering pump into the coagulation bath for solidification and stretching. The initially formed fungal fiber filaments are then repeatedly introduced into the displacement bath for solvent displacement and further stretching. The displaced fungal fiber filaments are heat-set to remove moisture, dried and wound to obtain continuous and uniform fungal filament fibers with excellent biocompatibility, a diameter of 10~500μm and a breaking strength ≥100MPa.
[0052] The coagulation bath is one or more of deionized water, ethyl acetate, alcohol, acetone, alkaline solution, and metal salt solution; the coagulation bath temperature is 80℃~100℃; the coagulation bath time is 15min~2h; and the coagulation stretching ratio is 10%~300%.
[0053] The displacement bath is one or more of deionized water, alcohol, alkaline solution, and metal salt solution.
[0054] The replacement bath temperature is 80℃~100℃; the replacement stretching ratio is 10%~300%; the replacement bath time is 5min~2h; and the number of replacements is 2~7.
[0055] Secondly, embodiments of this application provide a high-strength, highly biocompatible microbial fiber, prepared by the aforementioned technical solution.
[0056] The high-strength, highly biocompatible fungal fibers are combined and twisted, and the fungal fibers are parallelly gathered and directionally twisted to obtain fungal yarns with a diameter of 20μm~5mm that are structurally uniform, morphologically complete, and have stable performance.
[0057] In some embodiments, the number of twisted threads is 2 to 100, and the twisting parameter ranges from 150 to 500 twists / m. After the obtained fungal yarn is arranged in a regular manner, it can be woven into a fabric by machine or knitting.
[0058] The resulting fabrics can be used in fields such as home textiles, apparel textiles, medical textiles, industrial textiles, transportation textiles, and smart textiles.
[0059] The following are some specific embodiments. It should be noted that the embodiments described below are exemplary and are only used to explain this application, and should not be construed as limiting this application. Where specific techniques or conditions are not specified in the embodiments, they shall be performed in accordance with the techniques or conditions described in the literature in this field or according to the product instructions. Reagents or instruments whose manufacturers are not specified are all conventional products that can be obtained commercially.
[0060] I. Preparation Method Example 1 This embodiment provides a method for preparing high-strength, highly biocompatible fungal fibers, including the following steps: S1. Ganoderma lucidum mycelium was crushed and thoroughly mixed with an alkaline solution, then heated in a water bath for 3 hours (at 65°C) to remove soluble polysaccharides and glycoproteins from the fungal raw material. After cooling to room temperature, it was centrifuged to precipitate. Subsequently, the precipitate was freeze-dried at -80°C to obtain a fungal polymer material with a deacetylation rate of 88%. S2, the deacetylated fungal polymer material was fully dissolved in a mixed solvent of N,N-dimethylformamide and 1-ethyl-3-methylimidazolium acetate in a mass ratio of 2:8 at 120℃ and 500 rpm to obtain a 2% (w / w) Ganoderma lucidum mycelium polymer solution. The physical image is shown below. Figure 1 As shown.
[0061] S3, the fungal polymer solution obtained in step S2 is extruded from the spinneret into the coagulation bath by a metering pump to solidify and stretch into shape. The initially formed fungal fiber filaments are then repeatedly introduced into the displacement bath for solvent displacement. After three displacements, the filaments are further stretched. The displaced fungal fiber filaments are then heat-set to remove moisture, dried, and wound to obtain continuous and uniform fungal fiber filaments.
[0062] Figure 1 This is a photograph of the Ganoderma lucidum mycelium polymer solution in Example 1.
[0063] As can be seen, there are no precipitates, stratifications, or visible agglomerates in the sample system. Under laser irradiation, clear and continuous Tyndall beams are observed, indicating that the solute is uniformly dispersed in the solvent, the system is homogeneous and stable, and it has excellent dissolution and dispersion effects.
[0064] Figure 2 The image shown is an SEM image of the fungal fibers obtained in Example 1, magnified 1000 times.
[0065] As can be seen, the fiber axis is continuous and intact, the diameter is evenly distributed, and there are no obvious macroscopic structural defects such as breakage, splitting, or holes.
[0066] Figure 3The stress-strain curve of the fungal fibers prepared in Example 1 is shown.
[0067] Experiments show that the tensile breaking strength of the prepared fungal fibers can reach approximately 122 MPa, with a breaking elongation of approximately 15.5%. The curve shows a linear increase in the low strain range, corresponding to the elastic deformation stage of the material, reflecting the high elastic modulus of the material. With the increase of tensile strain, the stress continues to rise steadily without a significant yield plateau, exhibiting a significant strain hardening effect until the material fractures. This proves that the sample has both high strength and good resistance to deformation, demonstrating excellent mechanical properties.
[0068] Comparative Example 1 The main difference compared to Example 1 is that N,N-dimethylformamide was not used in the dispersant in step S2. The rest is largely the same as in Example 1 and will not be repeated here.
[0069] Figure 4 The stress-strain curve of the fungal fibers prepared in Comparative Example 1 is shown.
[0070] As can be seen, the prepared fungal fibers undergo a linear elastic deformation stage with a strain of approximately 5%, followed by a continuous yielding and slow strain hardening stage, with the curve exhibiting obvious sawtooth-like fluctuations. Its tensile strength is only about 18 MPa, and its elongation at break is about 32%, exhibiting overall characteristics of low strength but good plasticity.
[0071] Comparative Example 2 Compared to Example 1, the main difference is that in step S2, N,N-dimethylformamide is replaced with N,N-dimethylacetamide (DMAc), and N,N-dimethylacetamide and 1-ethyl-3-methylimidazolium acetate are mixed in a mass ratio of 3:7. The rest is largely the same as in Example 1 and will not be repeated here.
[0072] Figure 5 The stress-strain curve of the fungal fibers prepared in Comparative Example 2 is shown.
[0073] As can be seen, the stress-strain curve of the prepared fungal fiber exhibits an approximately linear continuous deformation characteristic with no obvious yield plateau. The stress increases uniformly with strain, and the curve is accompanied by significant sawtooth fluctuations throughout. Finally, instantaneous brittle fracture occurs at about 24% strain. Its tensile strength is about 20 MPa, and its elongation at break is about 24%. Overall, it exhibits mechanical properties of moderate strength and good ductility.
[0074] Comparative Example 3 The main difference compared to Example 1 is that in step S2, N,N-dimethylformamide is replaced with 1,3-dimethyl-2-imidazolinone (DMI), and 1,3-dimethyl-2-imidazolinone and 1-ethyl-3-methylimidazolium acetate are mixed in a mass ratio of 4:6. The rest is largely the same as in Example 1 and will not be repeated here.
[0075] Figure 6 The stress-strain curve of the fungal fibers prepared in Comparative Example 3 is shown.
[0076] As can be seen, the stress-strain curve of the prepared fungal fiber exhibits an approximately linear continuous deformation characteristic with no obvious yield plateau. The stress increases uniformly with strain, and the curve is accompanied by slight sawtooth fluctuations, eventually resulting in instantaneous brittle fracture at approximately 18% strain. Its tensile strength is approximately 25 MPa, and its elongation at break is approximately 18%, exhibiting overall mechanical properties of moderate strength and moderate ductility.
[0077] Comparative Example 4 The main difference compared to Example 1 is that in step S2, N,N-dimethylformamide is replaced with dimethyl sulfoxide (DMSO), and DMSO and 1-ethyl-3-methylimidazolium acetate are mixed in a 3:7 mass ratio. The rest is largely the same as in Example 1 and will not be repeated here.
[0078] Figure 7 The stress-strain curve of the fungal fibers prepared in Comparative Example 4 is shown.
[0079] As can be seen, the tensile strength of the prepared fungal fiber is about 58 MPa and the elongation at break is about 6.8%, exhibiting high strength and moderate ductility in mechanical behavior.
[0080] Comparing Example 1 with Comparative Examples 1-4, it can be seen that the fungal fibers prepared using DMF as a co-solvent exhibit the best tensile breaking properties. This may be because: DMF molecules are highly polar and have low steric hindrance; their carbonyl groups can form strong hydrogen bonds with the hydroxyl and amino groups of fungal polysaccharides, efficiently disrupting the original hydrogen bond network, allowing the molecular chains to fully extend and degrade less; furthermore, DMF is easily removed, and after molding, the polysaccharide chains can rebuild dense hydrogen bonds, resulting in a uniform fiber structure with few defects, thus exhibiting excellent mechanical strength.
[0081] The cell compatibility of the fungal fibers obtained in Example 1 and Comparative Examples 1-4 was evaluated, and the test results are as follows: Figure 8 As shown.
[0082] The testing method was as follows: the bacterial fibers were soaked in deionized water until the solvent was basically dissipated, and then the bacterial fibers were transferred to 75% disinfectant alcohol for disinfection. Subsequently, the disinfected bacterial fibers were rinsed several times with PBS buffer to remove the surface alcohol. The washed fibers were then soaked in culture medium for 12 hours to obtain bacterial fiber extract. Cells that had already adhered to the culture medium were added to the bacterial fiber extract and cultured for 24 hours. CCK-8 reagent was then added, and the absorbance was measured using an ELISA reader and the data were analyzed.
[0083] Figure 8 For the relative cell viability assay results, the viability of the blank control group (Control) cells was used as 100% baseline. The results showed that the relative cell viability of the test groups in Example 1 and Comparative Examples 1-4 was approximately 120%, which is far higher than the acceptable threshold of 80% for cell compatibility, and there was no significant cytotoxicity. The data of each group had small errors and good repeatability, proving that the above-mentioned test solvents have excellent cell compatibility under the experimental conditions.
[0084] Examples 2-3 and Comparative Example 5 Examples 2-3 and Comparative Example 5 provide a method for preparing fungal fibers. Compared with Example 1, the difference lies in that the fungal polymer materials with different deacetylation rates are obtained by controlling the water bath heating time (alkali treatment), as shown in Table 1 below. The rest is roughly the same as in Example 1, and will not be repeated here.
[0085] Table 1 Experiments show that high-strength, highly biocompatible microbial fibers can be successfully prepared in Examples 2-3.
[0086] High-strength fungal fibers with tensile strengths exceeding 100 MPa can be obtained when the deacetylation rate is within the range of 70% to 99%. The highest strength, reaching 122 MPa, is obtained when the deacetylation rate is 88%. The strengths of the fungal fibers obtained at deacetylation rates of 70% and 99% are 107 MPa and 110 MPa, respectively, maintaining a high strength level, with corresponding elongation at break of 17.4% and 12.0%. This indicates that the fungal fiber possesses excellent mechanical properties across a relatively wide deacetylation range, and that high strength can be maintained while fiber toughness can be controllably adjusted by regulating the deacetylation rate.
[0087] Examples 4-6 and Comparative Example 6 Examples 4-6 and Comparative Example 6 provide a method for preparing high-strength, highly biocompatible fungal fibers. The difference from Example 1 lies in the change of the mass fraction of the fungal polymer solution in step S2, as shown in Table 2 below. The rest is largely the same as in Example 1 and will not be repeated here.
[0088] Table 2 Experiments show that fungal fibers can be successfully prepared in Examples 4-6.
[0089] Within the range of 0.5% to 40% by mass fraction of the fungal polymer solution, as the mass fraction increases, the mixed solvent gradually reaches saturation in dissolving the fungal material, resulting in a gradual decrease in the solubility and strength of the obtained fungal fibers. When the mass fraction of the fungal polymer solution is below 0.5%, the fiber formability is poor, and the mechanical properties are unsatisfactory. When the mass fraction of the fungal polymer solution is between 50% and 40%, the fibers are difficult to fully dissolve in the dispersant and cannot be spun.
[0090] It should be noted that the fungal raw materials can be one or more of the following: Ganoderma lucidum, Trametes versicolor, Poria cocos, Polyporus umbellatus, Inonotus obliquus, and Lycoperdon perlatum.
[0091] Experiments show that the ionic liquid can be one or more of the following: 1-hexyl-3-methylimidazolium chloride, 1-octyl-3-methylimidazolium bromide, 1-butyl-2,3-dimethylimidazolium tetrafluoroborate, 1-methoxyethyl-3-methylimidazolium acetate, 1-hydroxyethyl-3-methylimidazolium chloride, 1-butyl-3-methylimidazolium chloride, 1-allyl-3-methylimidazolium chloride, 1-ethyl-3-methylimidazolium acetate, 1-butyl-3-methylimidazolium acetate, 1-allyl-3-methylimidazolium acetate, 1-(2-hydroxyethyl)-3-methylimidazolium acetate, 1-aminoethyl-3-methylimidazolium acetate, and 1-methoxyethyl-3-methylimidazolium acetate.
[0092] It should be noted that this application is not limited to the above-described embodiments. The above embodiments are merely examples, and any embodiments with the same structure and effect as the technical concept within the scope of this application are included in the technical scope of this application. Furthermore, various modifications that can be conceived by those skilled in the art to the embodiments, and other ways of constructing by combining some of the constituent elements of the embodiments, without departing from the spirit of this application, are also included in the scope of this application.
Claims
1. A method for preparing high-strength, highly biocompatible fungal fibers, characterized in that, Includes the following steps: S1, the crushed fungal raw materials are mixed with an alkaline solution and heated in a water bath to remove soluble polysaccharides and glycoproteins from the fungal raw materials. Then, after cooling to room temperature, they are centrifuged and precipitated. The precipitate is freeze-dried to obtain fungal polymer materials with a deacetylation rate of 70%~99%. S2, the fungal polymer material obtained in step S1 is fully dissolved in the dispersant at a temperature of 50℃~160℃ and a rotation speed of 500rpm~3000rpm to obtain a fungal polymer solution with a mass fraction of 0.5%~40%. The dispersant is a mixed solvent composed of an ionic liquid and a co-solvent N,N-dimethylformamide; The ionic liquid is one or more of the following: 1-hexyl-3-methylimidazolium chloride, 1-octyl-3-methylimidazolium bromide, 1-butyl-2,3-dimethylimidazolium tetrafluoroborate, 1-methoxyethyl-3-methylimidazolium acetate, 1-hydroxyethyl-3-methylimidazolium chloride, 1-butyl-3-methylimidazolium chloride, 1-allyl-3-methylimidazolium chloride, 1-ethyl-3-methylimidazolium acetate, 1-butyl-3-methylimidazolium acetate, 1-allyl-3-methylimidazolium acetate, 1-(2-hydroxyethyl)-3-methylimidazolium acetate, 1-aminoethyl-3-methylimidazolium acetate, and 1-methoxyethyl-3-methylimidazolium acetate. S3, the fungal polymer solution obtained in step S2 is extruded from the spinneret by a metering pump into the coagulation bath for solidification and stretching. The initially formed fungal fiber filaments are then repeatedly introduced into the displacement bath for solvent displacement and further stretching. The displaced fungal fiber filaments are heat-set to remove moisture, dried and wound to obtain continuous and uniform fungal filament fibers with excellent biocompatibility, a diameter of 10~500μm and a breaking strength ≥100MPa.
2. The method for preparing high-strength, highly biocompatible fungal fibers according to claim 1, characterized in that, In step S1, the deacetylation rate of the fungal polymer material is obtained by adjusting the heating time and temperature of the water bath.
3. The method for preparing high-strength, highly biocompatible fungal fibers according to claim 1, characterized in that, In step S1, the alkaline solution is one or more of lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium carbonate, and sodium bicarbonate, and the molar concentration of the alkaline solution is 5~13 mol / L.
4. The method for preparing high-strength, highly biocompatible fungal fibers according to claim 1, characterized in that, The water bath heating time is 30 minutes to 4 hours, and the temperature is 60℃ to 100℃.
5. The method for preparing high-strength, highly biocompatible fungal fibers according to claim 1, characterized in that, In the dispersant, the mass fraction of N,N-dimethylformamide is 10% to 60%.
6. The method for preparing high-strength, highly biocompatible fungal fibers according to claim 1, characterized in that, The fungal raw materials are processing by-products of medicinal fungi, and the medicinal fungi are Ganoderma lucidum, Trametes versicolor, Poria cocos, Polyporus umbellatus, Inonotus obliquus, or Lycoperdon perlatum.
7. The method for preparing high-strength, highly biocompatible fungal fibers according to claim 1, characterized in that, In step S3, the coagulation bath is one or more of deionized water, ethyl acetate, alcohols, acetone, alkaline solutions, and metal salt solutions; the coagulation bath temperature is 80℃~100℃; the coagulation bath time is 15min~2h; and the coagulation stretching ratio is 10%~300%.
8. The method for preparing high-strength, highly biocompatible fungal fibers according to claim 1, characterized in that, In step S3, the displacement bath is one or more of deionized water, alcohol, alkaline solution, and metal salt solution; the temperature of the displacement bath is 80℃~100℃; the displacement stretching ratio is 10%~300%; the displacement bath time is 5min~2h; and the number of displacements is 2~7.
9. A high-strength, highly biocompatible fungal fiber, characterized in that, It is prepared by the preparation method according to any one of claims 1-8.
10. An application of the high-strength, highly biocompatible fungal fiber as described in claim 9, characterized in that, The high-strength, highly biocompatible fungal fibers are combined and twisted to obtain fungal yarns with a diameter of 20μm~5mm that are structurally uniform, morphologically complete, and have stable performance.