A fiber spinning mother liquor containing Mg-MOF, its preparation method and fiber membrane

Abstract

This invention provides a fiber spinning mother liquor containing Mg-MOF, comprising: 0.01-5 parts by weight of Mg-MOF; 0.1-15 parts by weight of polyamino acids; 5-15 parts by weight of polyvinyl alcohol; 0.5-1.5 parts by weight of crosslinking agent; 0.1-10 parts by weight of acidic mucopolysaccharide and / or monosaccharide; and water to a total of 100 parts by weight. Compared with the prior art, the fiber spinning mother liquor provided by this invention contains Mg-MOF. The polyphenols and polyamino acids in its components can play an anti-inflammatory and antibacterial role, while Mg ions have the effect of promoting skin repair. Furthermore, Mg-MOF has a positive charge and can interact with the negatively charged spinning mother liquor through electrostatic interaction, so that Mg-MOF is uniformly dispersed in the spinning solution, which is more conducive to spinning and forming. The prepared fiber membrane has broad application prospects in wound healing, antibacterial repair, etc., greatly improving the application value of the material.

Description

Technical Field

[0001] This invention belongs to the field of biomaterials technology, and particularly relates to a fiber spinning mother liquor containing Mg-MOF, its preparation method and fiber membrane. Background Technology

[0002] Electrospinning is a highly efficient method for the continuous and large-scale production of polymer fibers. Based on its unique properties such as small pore size and controllable dimensions, it has broad development prospects and application value in the biomedical field. For example, when water is used as a solvent, direct high-voltage electrostatic filamentation and spraying onto wounds as a dressing has yielded good therapeutic effects. However, water has a high boiling point, making it difficult to form fibers. Adding other drugs to the spinning solution further destabilizes the spinning process, increasing the difficulty of fiber formation. Therefore, it is necessary to introduce materials that enhance the stability of the spinning solution into the mother liquor, while simultaneously endowing the silk-like mother liquor with new properties. Summary of the Invention

[0003] In view of this, the technical problem to be solved by the present invention is to provide a Mg-MOF-containing fiber spinning mother liquor with strong stability by utilizing electrostatic interaction, its preparation method and fiber membrane. The Mg-MOF-containing fiber spinning mother liquor provided by the present invention can obtain porous fiber materials through in-situ spinning technology, and can improve the antibacterial properties and repair characteristics of the materials.

[0004] This invention provides a fiber spinning mother liquor containing Mg-MOF, comprising:

[0005]

[0006] The organic ligands of the Mg-MOF are phenolic acid compounds.

[0007] Preferably, it also includes 0.01 to 5 parts by weight of a water-soluble chitosan derivative.

[0008] Preferably, the polyamino acid is selected from one or both of polylysine and polyarginine;

[0009] Preferably, the crosslinking agent is selected from one or more of citric acid, lactic acid, and acetic acid;

[0010] The acidic mucopolysaccharide and / or monosaccharide are selected from one or more of hyaluronic acid, glucose and fructose;

[0011] The water-soluble chitosan derivative is one or more of carboxymethyl chitosan, chitosan hydrochloride, chitosan quaternary ammonium salt, and chitosan lactate.

[0012] Preferably, the organic ligand of the Mg-MOF is 3,4,5-trihydroxybenzoic acid.

[0013] Preferably, the Mg-MOF is prepared according to the following steps:

[0014] S1) Mix phenolic acid compounds, magnesium salts and water, heat under reflux until the solution is clear, cool down and adjust the pH of the solution to alkaline to obtain an intermediate solution;

[0015] S2) The intermediate solution is subjected to a hydrothermal reaction to obtain Mg-MOF.

[0016] Preferably, the mass ratio of the phenolic acid compound to the magnesium salt is (2-5):(1-5);

[0017] The magnesium salt is selected from one or more of magnesium chloride, magnesium sulfate, and magnesium nitrate.

[0018] The pH value of the intermediate solution is 8 to 11.

[0019] Preferably, in step S1), the temperature of the heating reflux is 90°C to 110°C; and then the temperature is reduced to 40°C to 60°C.

[0020] The temperature of the hydrothermal reaction in step S2) is 100℃~150℃; the time of the hydrothermal reaction is 12~36h.

[0021] The present invention also provides a method for preparing the above-mentioned fiber spinning mother liquor, comprising the following steps:

[0022] A1) Mix polyvinyl alcohol with water to obtain a polyvinyl alcohol solution;

[0023] Acidic mucopolysaccharides and / or polysaccharides are mixed with water to obtain a sugar solution;

[0024] A2) After mixing Mg-MOF with sugar solution, polyamino acid, polyvinyl alcohol solution and crosslinking agent are added in sequence to obtain fiber spinning mother liquor.

[0025] The present invention also provides a fiber membrane obtained by spinning the above-mentioned fiber spinning mother liquor.

[0026] Preferably, the spinning voltage is 15-25kV; the spinning receiving distance is 8-15cm; and the flow rate of the fiber spinning mother liquor during spinning is 1-200μL / min.

[0027] This invention provides a fiber spinning mother liquor containing Mg-MOF, comprising: 0.01–5 parts by weight of Mg-MOF; 0.1–15 parts by weight of polyamino acids; 5–15 parts by weight of polyvinyl alcohol; 0.5–1.5 parts by weight of a crosslinking agent; 0.1–10 parts by weight of acidic mucopolysaccharides and / or monosaccharides; and water to a total of 100 parts by weight. Compared with the prior art, the fiber spinning mother liquor provided by this invention contains Mg-MOF. The polyphenols and polyamino acids in its components can play an anti-inflammatory and antibacterial role, while Mg ions have the effect of promoting skin repair. Furthermore, Mg-MOF has a positive charge and can interact with the negatively charged spinning mother liquor through electrostatic interaction, so that Mg-MOF is uniformly dispersed in the spinning solution, which is more conducive to spinning and forming. The prepared fiber membrane has broad application prospects in wound healing, antibacterial repair, etc., greatly improving the application value of the material.

[0028] Experimental results show that the fiber spinning mother liquor provided by this invention can be successfully used to prepare fiber materials through electrospinning, and exhibits excellent antibacterial properties. Attached Figure Description

[0029] Figure 1 This is a scanning electron microscope image of the Mg-MOF obtained in Example 1 of the present invention;

[0030] Figure 2 This is a scanning electron microscope image of the fiber membrane obtained in Example 1 of the present invention. Detailed Implementation

[0031] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. 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 of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0032] The present invention provides a fiber spinning masterbatch containing Mg-MOF, comprising: 0.01 to 5 parts by weight of Mg-MOF; 0.1 to 15 parts by weight of polyamino acids; 5 to 15 parts by weight of polyvinyl alcohol; 0.5 to 1.5 parts by weight of crosslinking agent; 0.1 to 10 parts by weight of acidic mucopolysaccharide and / or monosaccharide; and water to make up to 100 parts by weight.

[0033] According to the present invention, the content of Mg-MOF in the fiber spinning mother liquor is preferably 0.05-3 parts by weight, more preferably 0.05-2 parts by weight, even more preferably 0.05-1 parts by weight, and most preferably 0.1-0.5 parts by weight. Metal-organic frameworks (MOFs) are typical porous crystalline materials constructed by orderly splicing organic linkers between metal nodes. The unique framework and pore structure characteristics of MOF materials determine that they have unique characteristics such as large specific surface area, high porosity and chemical tunability, and have broad application prospects in wound treatment, drug release and other fields. The organic ligand of the Mg-MOF is preferably a phenolic acid compound, more preferably 3,4,5-trihydroxybenzoic acid. In the present invention, the Mg-MOF is preferably prepared according to the following steps: S1) Mix the phenolic acid compound, magnesium salt and water, heat and reflux until the solution is transparent, cool down, and adjust the pH of the solution to alkaline to obtain an intermediate solution; S2) Perform a hydrothermal reaction on the intermediate solution to obtain Mg-MOF. The preferred mass ratio of the phenolic acid compound to the magnesium salt is (2-5):(1-5), more preferably (3-4):(1-4), even more preferably (3-4):(1-3), even more preferably (3.5-4):(1-2), and most preferably 3.8:1. The magnesium salt can be any soluble magnesium salt known to those skilled in the art, and there are no special limitations. In this invention, it is preferably one or more of magnesium chloride, magnesium sulfate, and magnesium nitrate. The preferred mass ratio of the magnesium salt to water is (1-5):(30-100), more preferably (1-4):(30-80), even more preferably (1-3):(40-60), even more preferably (1-2):(45-55), and most preferably 1:50. The preferred heating and reflux temperature is 90℃-110℃, more preferably 95℃. The temperature is preferably 100℃, and more preferably 105℃. The reflux heating time is preferably 1-3 hours, more preferably 1.5-2.5 hours, and more preferably 2 hours. After reflux heating until the solution is transparent, the temperature is preferably lowered to 40℃-60℃, more preferably 45℃-55℃, and more preferably 55℃. Then, the pH of the solution is adjusted to alkaline. In this invention, an alkaline solution is preferably used to adjust the pH of the solution. The alkaline solution is preferably an aqueous solution of alkali metal hydroxide, more preferably an aqueous solution of potassium hydroxide and / or an aqueous solution of sodium hydroxide. The concentration of the alkaline solution is preferably 5-10 mol / L. The pH of the solution is adjusted to preferably 8-11, more preferably 8-10, to obtain an intermediate solution. The alkaline solution added in this invention acts as a catalyst and also has a key influence on the structure of the MOF material. By controlling the concentration and amount of alkaline solution as described above, this invention can avoid excessive influence on the reaction system, which is beneficial to achieving the optimal morphology and properties of the subsequent MOF.The intermediate solution is subjected to a hydrothermal reaction, preferably in a closed pressure vessel, more preferably in a reaction vessel; the reaction vessel can be any reaction vessel known to those skilled in the art and there are no special limitations, but in this invention, a polytetrafluoroethylene reaction vessel is preferred; the temperature of the hydrothermal reaction is preferably 100℃~150℃, more preferably 110℃~140℃, and even more preferably 120℃~130℃; the time of the hydrothermal reaction is preferably 12~36h, more preferably 18~28h, and even more preferably 24h; after the hydrothermal reaction, preferably after centrifugation and washing, Mg-MOF is obtained; the centrifugation speed is preferably 8000~12000rpm; the centrifugation time is preferably 5~10min; the centrifugation temperature is preferably 4℃~20℃; the washing is preferably performed with ethanol and water, more preferably by repeated cross-washing with ethanol and water until the solution is transparent and clear after centrifugation; after washing, drying is preferred; the drying method is preferably freeze drying. This invention adds Mg-MOF to the fiber spinning mother liquor. Mg-MOF exhibits good dispersibility in water and can react rapidly and degrade slowly in acidic environments, releasing magnesium ions and polyphenols. This introduces magnesium ions into the spinning process, which promote cell differentiation and wound healing. The decomposed polyphenols and polyamino acids have anti-inflammatory and antibacterial effects. Furthermore, the Mg-MOF added in this invention has a positive charge, which allows it to interact electrostatically with the negatively charged spinning mother liquor, enhancing the stability of the spinning solution.

[0034] According to the present invention, the content of polyvinyl alcohol in the fiber spinning mother liquor is preferably 5 to 12 parts by weight, more preferably 5 to 10 parts by weight, and even more preferably 5 to 8 parts by weight.

[0035] According to the present invention, the content of the polyamino acid in the fiber spinning mother liquor is preferably 0.5 to 10 parts by weight, more preferably 1 to 5 parts by weight, even more preferably 2 to 3 parts by weight, and most preferably 2.5 parts by weight; the polyamino acid is preferably polylysine and / or polyarginine; the molecular weight of the polyamino acid is preferably 3000 to 5000, more preferably 3500 to 4500, and even more preferably 3800 to 4200; polylysine, as a cationic polymer, has anti-inflammatory, antibacterial and bactericidal effects; the crosslinking degree of the mother liquor is improved through the hydrogen bond interaction between the polyamino acid and polyvinyl alcohol.

[0036] According to the present invention, the content of the crosslinking agent in the fiber spinning mother liquor is preferably 0.5 to 1.2 parts by weight, more preferably 0.5 to 1 part by weight, even more preferably 0.6 to 0.8 parts by weight, and most preferably 0.7 parts by weight; the crosslinking agent is preferably one or more of citric acid, lactic acid and acetic acid; the degree of crosslinking of the mother liquor is improved by the crosslinking agent and crosslinking with polyvinyl alcohol.

[0037] According to the present invention, the content of the acidic mucopolysaccharide and / or monosaccharide in the fiber spinning mother liquor is preferably 0.3 to 10 parts by weight, more preferably 0.3 to 10 parts by weight, even more preferably 0.5 to 10 parts by weight, and most preferably 1 to 10 parts by weight; the acidic mucopolysaccharide is preferably hyaluronic acid; the monosaccharide is preferably glucose and / or fructose; the acidic mucopolysaccharide and monosaccharide have moisturizing and repairing functions, and their addition to the fiber spinning mother liquor can enhance the affinity of the fiber spinning mother liquor for Mg-MOF through electrostatic interaction, further enhancing the stability of the fiber spinning mother liquor, which is more conducive to spinning formation.

[0038] According to the present invention, the fiber spinning mother liquor preferably further includes 0.01 to 5 parts by weight of a water-soluble chitosan derivative, more preferably 0.05 to 3 parts by weight of a water-soluble chitosan derivative, even more preferably 0.05 to 1 part by weight of a water-soluble chitosan derivative, and most preferably 0.1 to 0.5 parts by weight of a water-soluble chitosan derivative; the water-soluble chitosan derivative is preferably one or more of carboxymethyl chitosan, chitosan hydrochloride, chitosan quaternary ammonium salt, and chitosan lactate; the water-soluble chitosan derivative has antibacterial and anti-inflammatory effects, thereby improving the antibacterial and anti-inflammatory ability of the prepared fiber membrane.

[0039] According to the present invention, the remaining components of the fiber spinning mother liquor are water, which is used to reduce the amount to less than 100 parts by weight.

[0040] This invention provides a fiber spinning mother liquor containing Mg-MOF, which exhibits good dispersibility in water and responds rapidly and decomposes slowly in acidic environments. The decomposed polyphenols and polyamino acids can play an anti-inflammatory and antibacterial role, while Mg ions can promote cell migration and vascular repair. Furthermore, Mg-MOF has a positive charge and can interact with the negatively charged spinning mother liquor through electrostatic interaction, enhancing the stability of the spinning solution and facilitating spinning formation. The prepared fiber membrane has broad application prospects in wound healing, antibacterial repair, and other aspects, greatly improving the application value of the material.

[0041] The present invention also provides a method for preparing the above-mentioned fiber spinning mother liquor, comprising the following steps: A1) mixing polyvinyl alcohol with water to obtain a polyvinyl alcohol solution; mixing acidic mucopolysaccharide and / or monosaccharide with water to obtain a sugar solution; A2) mixing Mg-MOF with the sugar solution, and then sequentially adding polyamino acid, polyvinyl alcohol solution and crosslinking agent, and mixing evenly to obtain the fiber spinning mother liquor.

[0042] In this invention, there are no special restrictions on the source of any raw materials; commercially available materials are acceptable. The types and contents of polyvinyl alcohol, polyamino acids, acidic mucopolysaccharides and / or monosaccharides, Mg-MOF and crosslinking agents are the same as described above and will not be repeated here.

[0043] Polyvinyl alcohol is mixed with water to obtain a polyvinyl alcohol solution; the mass concentration of the polyvinyl alcohol solution is preferably 5% to 15%, more preferably 8% to 12%, and even more preferably 10%.

[0044] Acidic mucopolysaccharides and / or monosaccharides are mixed with water to obtain a sugar solution; the mass concentration of the sugar solution is preferably 1% to 5%, more preferably 1% to 3%, and even more preferably 2%.

[0045] Mix Mg-MOF with a sugar solution; preferably, add a water-soluble chitosan derivative; the type and content of the water-soluble chitosan derivative are the same as described above, and will not be repeated here; the mixing method can be any method known to those skilled in the art, and there are no special restrictions. Ultrasonic mixing is preferred in this invention.

[0046] Then, polyamino acids, polyvinyl alcohol solution, and crosslinking agent are added sequentially. In this invention, it is preferred to add polyamino acids first and mix, then add polyvinyl alcohol solution and mix, and finally add crosslinking agent and continue mixing. The mixing time after adding polylysine is preferably 5-20 min, more preferably 10-20 min, and even more preferably 15 min. The mixing time after adding polyvinyl alcohol solution is preferably 5-30 min, more preferably 10-20 min, and even more preferably 15 min. The mixing method is preferably ultrasound. The power of the ultrasound is preferably 200-400 W, more preferably 300 W. The continued mixing time is preferably 5-30 min, more preferably 10-20 min, and even more preferably 15 min. The continued mixing method is preferably ultrasound. The power of the ultrasound is preferably 200-400 W, more preferably 300 W.

[0047] After adding polyamino acid, polyvinyl alcohol solution and crosslinking agent, it is preferably allowed to stand to obtain fiber spinning mother liquor; the standing temperature is preferably 4℃~10℃, more preferably 4℃~6℃; the standing time is preferably 1~4h, more preferably 2~3h.

[0048] The present invention also provides a fiber membrane obtained by spinning fiber spinning mother liquor.

[0049] The fiber mother liquor provided by this invention can be used to obtain porous fiber materials through in-situ spinning technology, and can improve the antibacterial properties and repair characteristics of the materials.

[0050] According to the present invention, the spinning method can be any method known to those skilled in the art and there are no special limitations. In the present invention, electrospinning is preferred.

[0051] According to the present invention, the spinning voltage is preferably 15-25kV; specifically, the spinning voltage can be 15kV, 16kV, 17kV, 18kV, 19kV, 20kV, 21kV, 22kV, 23kV, 24kV or 25kV.

[0052] According to the present invention, the receiving distance of the spinning is preferably 8 to 15 cm; specifically, it can be 8 cm, 10 cm, 12 cm, 14 cm or 15 cm.

[0053] According to the present invention, the flow rate of the fiber spinning mother liquor during spinning is preferably 1 to 200 μL / min; specifically, it can be 1 μL / min, 5 μL / min, 10 μL / min, 50 μL / min, 80 μL / min, 100 μL / min, 150 μL / min or 200 μL / min.

[0054] This invention, through specific component screening and combination, enables the instantaneous processing of porous nanofiber materials using water as a solvent and in-situ electrospinning, without the need for post-processing. This successfully prepares a multifunctional fiber membrane with good adhesion. Through spinning, the membrane can promptly cover and protect wounds from external infection. It can be used as an antibacterial fiber membrane product without post-processing, providing a new strategy for antibacterial treatment.

[0055] To further illustrate the present invention, the following describes in detail, with reference to embodiments, a fiber spinning mother liquor containing Mg-MOF, its preparation method, and the fiber membrane provided by the present invention.

[0056] All reagents used in the following examples are commercially available. Polyvinyl alcohol used in the examples was from Aladdin Reagent (Shanghai) Co., Ltd., catalog number P119364-250g, with a molecular weight of 67,000; polylysine was from Beijing Innocare Technology Co., Ltd., catalog number A18267, with a molecular weight of 3800-4200; hyaluronic acid was from Shanghai Maclean Biochemical Technology Co., Ltd., catalog number H909936-100g, with a molecular weight of 100,000-200,000; and carboxymethyl chitosan was from Shanghai Jizhi Biochemical Technology Co., Ltd., catalog number C51060-100g, wherein the degree of carboxyl substitution in the chitosan was greater than 80%.

[0057] Example 1

[0058] 1.1 Preparation of Mg-MOF

[0059] S1) Mix 3.8g gallic acid, 1g anhydrous magnesium chloride and 50mL water, then heat to 100℃ and react for 2h. After the solution becomes transparent, cool to 50℃ and adjust the pH of the solution to 8 with KOH (10mol / L) solution.

[0060] S2) The reaction solution was added to a 100 mL polytetrafluoroethylene reactor and reacted at 120 °C for 24 h in a sealed pressure vessel by hydrothermal method. After returning to room temperature, the separated product was separated by centrifugation, washed several times with deionized water, and then freeze-dried to obtain Mg-MOF.

[0061] 1.2 Fiber spinning mother liquor

[0062] Composition of fiber spinning mother liquor:

[0063]

[0064] Preparation of fiber spinning mother liquor:

[0065] First, prepare a 10% polyvinyl alcohol aqueous solution and a 2% hyaluronic acid solution. Then, weigh 2 mg of Mg-MOF and 2 mg of carboxymethyl chitosan and add them to 1 ml of the prepared hyaluronic acid solution. After ultrasonic dispersion, add 50 mg of polylysine and ultrasonicate (300 W) for 15 minutes. Then, add 1 mL of the prepared polyvinyl alcohol solution and ultrasonicate for another 15 minutes. Add 15 mg of citric acid and ultrasonicate for another 15 minutes. Then, let it stand in a refrigerator at 4°C for 2 hours.

[0066] 1.3 Preparation of Fiber Membranes

[0067] Add the fiber mother liquor to a 5mL syringe, install it into the electrospinning device, turn on the power switch, and adjust the machine parameters to perform electrospinning (voltage 25kV, receiving distance 15cm, mother liquor flow rate 10μL / min, using a roller with a diameter of 100mm and a length of 200mm as a collecting device, attaching tin foil to the roller, and during the fiber collection process, the roller speed is 120rpm, and the effective length of fiber collected on the roller is 100mm) to obtain a fiber membrane.

[0068] The Mg-MOF obtained in Example 1 was analyzed using scanning electron microscopy, and its scanning electron micrograph is shown below. Figure 1 As shown.

[0069] The fiber membrane obtained in Example 1 was analyzed using a scanning electron microscope, and its scanning electron microscope image is shown below. Figure 2 As shown.

[0070] The zeta potential in aqueous solution was measured using electrophoretic light scattering technology with a Malvern ZS-90 analyzer. The surface potentials of the hyaluronic acid used in Example 1 and the Mg-MOF obtained in Example 1 were analyzed, and the results are shown in Table 1.

[0071] Table 1 Surface potential test results

[0072] Surface potential Hyaluronic acid -23mV Mg-MOF 0.6mV

[0073] Example 2

[0074] The preparation was carried out according to Example 1, except that the hydrothermal reaction conditions in step S2) during the preparation of Mg-MOF were controlled as follows: temperature 100℃, time 12h.

[0075] Example 3

[0076] Prepared according to Example 1, except that in the process of preparing Mg-MOF, the pH of the solution in step S1) is adjusted to 10.

[0077] Example 4

[0078] Prepared according to Example 1, except that the concentration of the hyaluronic acid solution prepared during the preparation of the fiber mother liquor was 1%.

[0079] Antibacterial test

[0080] Test Procedure: The fiber membranes prepared in Examples 1-4 were dispersed in autoclaved agar and mixed thoroughly to a final concentration of 1 mg / mL. Agar culture plates were then prepared, with a control group containing the same concentration of dimethyl sulfoxide solvent in the agar. Uniformly grown bacterial pellets (5 mm in diameter) were punched from the edge of the colonies and inoculated into the center of the plate. The agar plates were then incubated at 37°C for approximately 18-24 hours, until the control group colonies completely covered the culture dish. The colony diameter of each treatment group was measured using the cross-sectional method, and the inhibition rate was calculated. The test results are shown in Table 2.

[0081] Table 2. Antibacterial performance test results of each embodiment.

[0082] Antibacterial rate (%) Example 1 70 Example 2 68 Example 3 63 Example 4 65

[0083] The preferred embodiments of the present invention disclosed above are merely for illustrating the present invention, and the present invention is not limited thereto. Those skilled in the art will understand that, within the scope of the present invention's concept, modifications can be made to the technical solutions of the present invention, or some technical features can be combined in any other way. Such modifications or combinations do not cause the essence of the corresponding technical solutions to depart from the spirit and scope of the various embodiments of the present invention, and should be considered as the content disclosed in the present invention, all of which fall within the protection scope of the present invention.

Claims

1. A fiber spinning dope containing Mg-MOF, characterized in that, Comprising: Mg-MOF 0.01~5 parts by weight; Polyamino acid 0.1~15 parts by weight Polyvinyl alcohol 5~15 parts by weight; Crosslinking agent 0.5~1.5 parts by weight; Acid mucopolysaccharide and / or monosaccharide 0.1~10 parts by weight; Water supplemented to 100 parts by weight; The organic ligand of the Mg-MOF is a phenolic acid compound; Further comprising water-soluble chitosan derivative 0.01~5 parts by weight; The polyamino acid is one or both of polylysine and polyarginine; The crosslinking agent is selected from one or more of citric acid, lactic acid and acetic acid; The acid mucopolysaccharide and / or monosaccharide is selected from one or more of hyaluronic acid, glucose and fructose; The water-soluble chitosan derivative is one or more of carboxymethyl chitosan, chitosan hydrochloride, chitosan quaternary ammonium salt and chitosan lactate; The organic ligand of the Mg-MOF is 3,4,5-trihydroxybenzoic acid.

2. The fiber spinning dope according to claim 1, characterized in that, The Mg-MOF is prepared according to the following steps: S1) mixing a phenolic acid compound, a magnesium salt and water, heating to reflux until the solution is transparent, cooling, adjusting the pH value of the solution to be alkaline, to obtain an intermediate solution; S2) hydrothermal reaction of the intermediate solution to obtain the Mg-MOF.

3. The fiber spinning dope according to claim 2, characterized in that, The mass ratio of the phenolic acid compound to the magnesium salt is (2~5):(1~5); The magnesium salt is selected from one or more of magnesium chloride, magnesium sulfate and magnesium nitrate; The pH value of the intermediate solution is 8~11.

4. The fiber spinning dope of claim 2, wherein, The temperature of heating to reflux in step S1) is 90℃~110℃; the temperature is cooled to 40℃~60℃; The temperature of hydrothermal reaction in step S2) is 100℃~150℃; the time of hydrothermal reaction is 12~36 h.

5. The method of producing a fiber spinning dope according to claim 1, characterized in that, Comprising the following steps: A1) mixing polyvinyl alcohol and water to obtain a polyvinyl alcohol solution; Mixing acid mucopolysaccharide and / or monosaccharide and water to obtain a sugar solution; A2) mixing Mg-MOF and the sugar solution, then sequentially adding polyamino acid, polyvinyl alcohol solution and crosslinking agent to obtain a fiber spinning mother liquor.

6. A fibrous membrane characterized by, The fiber spinning mother liquor of any one of claims 1~4 or prepared by the preparation method of claim 5 is obtained by spinning.

7. The fibrous membrane according to claim 6, characterized in that The voltage of spinning is 15~25 kV; the receiving distance of spinning is 8~15 cm; the flow rate of the fiber spinning mother liquor during spinning is 1~200 μL / min.

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