A bio-based nanofiber membrane, a preparation method thereof and application thereof in ethylene adsorption and fruit preservation

Abstract

The application discloses a kind of bio-based nanofiber membrane and its preparation method and application in ethylene adsorption and fruit preservation;The application is by dispersing oxidized starch and pullulan in water, and is configured into the mixed solution of oxidized starch / pullulan with solute mass fraction of 15~30%, and starch-polyose compound paste solution is obtained by gelatinization;Add water-soluble protein, heat and stir to obtain electrospinning liquid;The electrospinning liquid is electrospun to obtain bio-based nanofiber membrane.The bio-based nanofiber membrane prepared by the application can adsorb ethylene gas in the environment under normal temperature and pressure as a green material, and has low cost, simple process and can be reused.The nanofiber membrane system prepared by selecting oxidized starch-pullulan-water-soluble protein can adsorb 3.19-15.40cm 3 / g ethylene gas under normal temperature and pressure, prolongs the shelf life of food, and comprehensively realizes the preservation of banana and other respiratory-peak fruits.

Description

Technical Field

[0001] This invention belongs to the fields of food and chemical technology, specifically relating to a bio-based nanofiber membrane, its preparation method, and its application in ethylene adsorption and fruit preservation. Background Technology

[0002] Ethylene (C2H4) is a pure unsaturated hydrocarbon and a volatile plant hormone. This hormone, produced by higher plants, activates and controls plant physiological mechanisms and development, regulating plant growth, ripening, and senescence. Studies have shown that postharvest quality deterioration and loss of fruits and vegetables are mainly caused by ethylene over-ripening and microbial contamination. Reducing ethylene content in a sealed atmosphere helps in the storage and preservation of agricultural products. Packaging containing active substances can inhibit the adverse effects of ethylene gas and prevent microbial growth. In practical applications, ethylene adsorbents and scavengers are needed to replace chemical reagents and disinfectants to extend the shelf life of fruits and vegetables.

[0003] Ethylene removers are packaged in bags, films, and boxes. The most common form is granular or powdery substances packaged in bags. Ethylene adsorbents and removers in film form have been less studied. Adsorbents react with ethylene through physical or chemical adsorption. Ethylene regulation methods can be divided into three types: (1) improving modified atmosphere packaging and reducing ethylene by exchanging different gases in the headspace; (2) using microporous packaging materials to allow gases to permeate outside the packaging; and (3) using ethylene adsorbents / removers to remove ethylene. Ethylene removers (chemical reaction) and ethylene adsorbents (physical adsorption) have been applied in large supermarket chains to reduce food spoilage and extend shelf life, such as the fresh fruit and vegetable packaging of Tesco and M&S. CN109503973B discloses a method for preparing a preservation film with ethylene adsorption function. The preservation film is prepared by mixing styrene, hydroxyethyl methacrylate, methacrylic anhydride, and freeze-dried bacterial powder, followed by casting and heat drying. The freeze-dried bacterial powder of Mycobacterium roximate catalyzes the epoxidation of ethylene and fixes it onto a specific carrier. This type of preservation film can absorb ethylene from stored fruits and vegetables, but direct contact with the fruits and vegetables may leave chemical residues that could have toxic side effects on the human body, and the byproducts of its degradation process can also pollute the environment. CN114052068A discloses a biofilm with ethylene adsorption properties. This biofilm uses an ultrasonically modified zein-acetic acid solution (50%–90%), which is cast, heated, and dried to form the film. The adsorption rate for ethylene is 5.67–12.54 ppm / h, achieving preservation of fruits with climacteric respiration. Although the above patent achieves fruit preservation through modification of zein, it suffers from problems such as the use and handling of high-concentration reagents and insufficient safety during the production process.

[0004] Electrospinning, a technology for producing micron- and nano-sized fibers, has attracted widespread attention due to its simplicity, low cost, and high functionality. Nanofibers possess advantages such as large specific surface area, low density, good mechanical properties, and high porosity, making them ideal materials for biomedicine, energy storage, environmental filtration, and textiles. Electrospinning technology uses single or composite components of biopolymers (polysaccharides and proteins), composite metals, and metal oxides as raw materials to prepare nanofibers with specific functions.

[0005] Due to current social and environmental needs, bio-based fibers prepared by electrospinning have attracted widespread attention. Polysaccharides and proteins possess biodegradability and biocompatibility, making them applicable in environmental and medical fields. While significant progress has been made in the application of bio-based materials for food packaging, research on bio-based nanofiber membranes with ethylene adsorption capabilities is relatively limited. Summary of the Invention

[0006] To address the shortcomings of existing technologies, the present invention aims to provide a bio-based nanofiber membrane that is simple to operate, time-saving, low-cost, and has uniform fiber size and pore size, as well as its preparation method and its application in ethylene adsorption and fruit preservation. The nanofiber membrane of the present invention can significantly improve ethylene adsorption performance.

[0007] This invention develops a low-cost, high-adsorption-performance bio-based nanofiber membrane using oxidized starch-polysaccharide-protein complex as raw material, thereby realizing the high-value utilization of biomass resources and promoting the development of small molecule gas adsorption technology.

[0008] The objective of this invention is achieved through the following technical solution:

[0009] The first aspect of this application provides a method for preparing a bio-based nanofiber membrane, comprising the following steps:

[0010] (1) Disperse oxidized starch and pullulan in water to prepare a mixed solution of oxidized starch / pullulan with a solute mass fraction of 15-30%, and gelatinize it to obtain a starch-polysaccharide complex gelatinized solution;

[0011] (2) Add water-soluble protein to the starch-polysaccharide complex gelatinized solution obtained in step (1), heat and stir to mix to obtain electrospinning solution;

[0012] (3) Electrospinning the electrospinning solution obtained in step (2) to obtain a bio-based nanofiber membrane.

[0013] Preferably, in step (1), the carboxyl content of the oxidized starch is 0.08% to 0.64%;

[0014] More preferably, the oxidized starch has a carboxyl content of 0.35% to 0.45%;

[0015] Preferably, in step (1), the oxidized starch is oxidized starch prepared by wet oxidation of starch with hydrogen peroxide and / or sodium hypochlorite.

[0016] More preferably, the method for preparing the oxidized starch is as follows: using hydrogen peroxide and / or sodium hypochlorite as oxidant and copper sulfate as catalyst, starch is oxidized to obtain oxidized starch;

[0017] More preferably, the starch is at least one of corn starch, potato starch, and cassava starch; the mass ratio of copper sulfate to starch is 0.01 to 0.1%; the hydrogen peroxide and / or sodium hypochlorite account for 24.75 to 33% of the starch mass (calculated based on the density of a 30% hydrogen peroxide solution with a mass concentration of 1.1 g / mL in the example); the oxidation treatment temperature is 30 to 50°C, and the time is 2 to 4 hours.

[0018] Preferably, in step (1), the mass ratio of oxidized starch to pullulan in the oxidized starch / pullulan mixed solution is 3:1 to 1:3.

[0019] Preferably, in step (1), the gelatinization is carried out in a boiling water bath for 0.5 to 1.5 hours.

[0020] Preferably, in step (2), the water-soluble protein is one or more of soy protein isolate, silk fibroin, rice protein and bovine hemoglobin.

[0021] More preferably, in step (2), the mass of the water-soluble protein is 0.5 to 3% of the total mass of oxidized starch and pullulan.

[0022] Preferably, in step (2), the solvent of the electrospinning solution is water.

[0023] Preferably, in step (2), the temperature of heating and stirring is 50-60°C.

[0024] Preferably, in step (3), the ambient temperature for electrospinning is 20–35°C and the ambient humidity is 25%–40%.

[0025] Preferably, in step (3), the needle used for electrospinning is No. 18 to No. 23, and the spinning time is 3 to 7 hours.

[0026] Preferably, in step (3), the conditions for electrospinning are: voltage of 12-24kV, receiving distance of 5-25cm, and injection speed of 0.5-2.5mL / h.

[0027] More preferably, the receiving distance is 13-22cm.

[0028] The second aspect of the present invention also provides an oxidized starch-polysaccharide-protein composite bio-based nanofiber membrane prepared by the above preparation method.

[0029] A third aspect of this invention also provides the application of the above-mentioned bio-based nanofiber membrane in ethylene adsorption and fruit preservation, particularly for vegetable preservation.

[0030] It should be noted that the oxidized starch-polysaccharide-protein composite bio-based nanofiber membrane provided by the present invention has a certain specific surface area and porosity, as well as a certain thickness and mechanical properties, and is therefore applicable to the field of small molecule gas adsorption materials, thereby improving the adsorption effect.

[0031] This invention provides an oxidized starch-polysaccharide-protein composite bio-based nanofiber membrane, its preparation method, and its application. The preparation method includes first gelatinizing oxidized pretreated starch with pullulan, adding water-soluble protein to the composite solution to obtain a composite electrospinning solution, and then performing electrospinning to obtain the bio-based nanofiber membrane. The addition of pullulan as a spinning aid reduces the surface tension of the spinning solution during electrospinning, which is beneficial for the spinning solution to break through the critical voltage during electrospinning, forming uniform and continuous nanofibers, resulting in an electrospun nanofiber membrane with certain porosity and flexibility. This solves the technical problems of low spinning efficiency and poor macroscopic and microscopic morphology of pure bio-based nanofiber membranes in existing electrospinning processes for preparing starch and protein nanofiber membranes. Furthermore, this invention has a simple preparation process, low cost, and is easy to operate.

[0032] Compared with the prior art, the advantages of the present invention are as follows:

[0033] (1) The present invention provides a method for preparing nanofiber membranes by electrostatic blending of protein / oxidized starch / pullulan polysaccharide. Starch is used as one of the raw materials for preparing nanofiber membranes. Starch is abundant, safe and non-toxic, which reduces the cost of use and improves the ethylene adsorption performance.

[0034] (2) This invention utilizes electrostatic blending of oxidized starch, polysaccharides, and proteins to prepare nanofiber membranes, overcoming the defect of poor spinnability of biomass starch and proteins themselves. The prepared bio-based nanofibers have uniform diameters, good morphological characteristics, and applicability.

[0035] (3) This invention utilizes the synergistic effect of the porous structure and high specific surface area of ​​nanofiber membranes with the multiple functional groups of proteins to achieve the preparation of biomass nanofiber membranes and the atmospheric pressure adsorption of ethylene (3.19-15.40 cm⁻¹) without the addition of chemical reagents. 3 / g). Attached Figure Description

[0036] Figure 1The images show the appearance and microstructure of the nanofiber membranes obtained in Example 1 and Comparative Example 1.

[0037] Figure 2 The ethylene adsorption capacity of the nanofiber system and protein powder system obtained in Examples 1, 2, 3, 4 and Comparative Examples 2, 3, and 4 is shown.

[0038] Figure 3 The images show the preservation effects of the oxidized starch-pullulan-protein nanofiber systems obtained in Examples 1, 2, 3, and 4, and the oxidized starch / pullulan nanofiber membrane obtained in Comparative Example 2. Detailed Implementation

[0039] To better understand the present invention, the following description, in conjunction with embodiments, further illustrates the present invention. However, the scope of protection claimed by the present invention is not limited to the scope described in the embodiments.

[0040] The morphology of the bio-based nanofiber membrane was observed using the following method: the obtained nanofiber membrane was adhered to a stage with conductive double-sided adhesive, and then the morphology of the membrane was observed by scanning electron microscopy.

[0041] In this example, the ethylene content in the bio-based nanofiber membrane was determined as follows: A certain amount of the nanofiber membrane (30 mg) was placed in a headspace vial, 1 mL of 0.1 M sodium hydroxide solution was added, and the cap was quickly tightened. The vial was stirred overnight at 400 rpm to completely destroy the bubble or bubble gel structure, allowing the ethylene to be fully released. The ethylene content was then determined using headspace gas chromatography. The gas chromatograph was equipped with a flame ionization detector (FID) and a DB-5 column (30 m × 0.32 mm × 0.25 μm), with high-purity nitrogen as the carrier gas and a flow rate of 40 mL / min. The headspace sampler test conditions were: oven temperature 60 °C, injection temperature 250 °C, and headspace vial pressurization time 0.2 min. The peak area of ​​ethylene was converted to ethylene concentration based on the ethylene standard.

[0042] Example 1

[0043] (1) Dissolve 20g of starch (cassava starch) in distilled water to prepare a starch milk with a mass concentration of 40%. Add copper sulfate (0.04wt%, relative to the amount of starch), adjust the pH to 8.35 with 1M sodium hydroxide solution, stir evenly, add 15mL of hydrogen peroxide solution (mass concentration of 30%), stir at a constant speed at 45℃ for 4h, add 5mL of sodium bisulfite solution (mass concentration of 10%) to terminate the reaction, adjust the pH to 7 with 1M sodium hydroxide solution, filter, wash 5 times, and dry at 45℃ to obtain oxidized starch (carboxyl content of 0.35%).

[0044] (2) The oxidized starch obtained in step (1) is mixed with pullulan polysaccharide at a mass ratio of 2:1 and dispersed in distilled water to prepare an oxidized starch / pullulan polysaccharide mixed aqueous solution with a total dry matter mass fraction of 20%. The solution is then stirred in a boiling water bath for 1 hour to obtain a composite gelatinized solution.

[0045] (3) Add 1% (percentage of the total dry matter of oxidized starch and pullulan) of soy protein isolate to the composite gelatinized solution obtained in step (2) and stir magnetically at 60°C for 1 hour to obtain an electrospinning solution.

[0046] (4) The electrospinning solution obtained in step (3) was electrospinned at an electrospinning voltage of 18kV, a spinning distance of 15cm, and a spinning solution driving speed of 1.5mL / h to prepare an oxidized starch / pullulan polysaccharide / soy protein isolate nanofiber membrane.

[0047] (5) Place the bio-based nanofiber membrane obtained in step (4) into a sealed container filled with ethylene gas and adsorb it at room temperature and pressure for 12 hours.

[0048] Example 2

[0049] (1) Dissolve 20g of starch (cassava starch) in distilled water to prepare a starch milk with a mass concentration of 40%. Add copper sulfate (0.04wt%, relative to the amount of starch), adjust the pH to 8.35 with 1M sodium hydroxide solution, stir evenly, add 15mL of hydrogen peroxide solution (mass concentration of 30%), stir at a constant speed at 45℃ for 4h, add 5mL of sodium bisulfite solution (mass concentration of 10%) to terminate the reaction, adjust the pH to 7 with 1M sodium hydroxide solution, filter, wash 5 times, and dry at 45℃ to obtain oxidized starch (carboxyl content of 0.35%).

[0050] (2) The oxidized starch obtained in step (1) is mixed with pullulan polysaccharide at a mass ratio of 1:1 and dispersed in distilled water to prepare an oxidized starch / pullulan polysaccharide mixed aqueous solution with a total dry matter mass fraction of 20%. The solution is then stirred in a boiling water bath for 1 hour to obtain a composite gelatinized solution.

[0051] (3) Add 1% (percentage of the total dry matter of oxidized starch and pullulan) of silk fibroin to the composite gelatinized solution obtained in step (2) and stir magnetically at 60°C for 1 hour to obtain an electrospinning solution.

[0052] (4) The electrospinning solution obtained in step (3) was electrospinned at an electrospinning voltage of 19kV, a spinning distance of 15cm, and a spinning solution driving speed of 1mL / h to prepare an oxidized starch / pullulan polysaccharide / silk fibroin nanofiber membrane.

[0053] (5) Place the bio-based nanofiber membrane obtained in step (4) into a sealed container filled with ethylene gas and adsorb it at room temperature and pressure for 12 hours.

[0054] Example 3

[0055] (1) Dissolve 20g of starch (cassava starch) in distilled water to prepare a starch milk with a mass concentration of 40%. Add copper sulfate (0.04wt%, relative to the amount of starch), adjust the pH to 8.35 with 1M sodium hydroxide solution, stir evenly, add 15mL of hydrogen peroxide solution (mass concentration of 30%), stir at a constant speed at 45℃ for 4h, add 5mL of sodium bisulfite solution (mass concentration of 10%) to terminate the reaction, adjust the pH to 7 with 1M sodium hydroxide solution, filter, wash 5 times, and dry at 45℃ to obtain oxidized starch (carboxyl content of 0.35%).

[0056] (2) The oxidized starch obtained in step (1) is mixed with pullulan polysaccharide at a mass ratio of 1:2 and dispersed in distilled water to prepare an oxidized starch / pullulan polysaccharide mixed aqueous solution with a total dry matter mass fraction of 25%. The solution is then stirred in a boiling water bath for 1 hour to obtain a composite gelatinized solution.

[0057] (3) Add rice protein with a mass fraction of 1% (the percentage of the total dry matter of oxidized starch and pullulan) to the composite gelatinized solution obtained in step (2), and stir magnetically at 60°C for 1 hour to obtain an electrospinning solution;

[0058] (4) The electrospinning solution obtained in step (3) was electrospinned at an electrospinning voltage of 18kV, a spinning distance of 18cm, and a spinning solution driving speed of 1mL / h to prepare an oxidized starch / pullulan polysaccharide / rice protein nanofiber membrane.

[0059] (5) Place the bio-based nanofiber membrane obtained in step (4) into a sealed container filled with ethylene gas and adsorb it at room temperature and pressure for 12 hours.

[0060] Example 4

[0061] (1) Dissolve 20g of starch (cassava starch) in distilled water to prepare a starch milk with a mass concentration of 40%. Add copper sulfate (0.04wt%, relative to the amount of starch), adjust the pH to 8.35 with 1M sodium hydroxide solution, stir evenly, add 15mL of hydrogen peroxide solution (mass concentration of 30%), stir at a constant speed at 45℃ for 4h, add 5mL of sodium bisulfite solution (mass concentration of 10%) to terminate the reaction, adjust the pH to 7 with 1M sodium hydroxide solution, filter, wash 5 times, and dry at 45℃ to obtain oxidized starch (carboxyl content of 0.35%).

[0062] (2) The oxidized starch obtained in step (1) is mixed with pullulan polysaccharide at a mass ratio of 1:1 and dispersed in distilled water to prepare an oxidized starch / pullulan polysaccharide mixed aqueous solution with a total dry matter mass fraction of 30%. The solution is then stirred in a boiling water bath for 1 hour to obtain a composite gelatinized solution.

[0063] (3) Add bovine hemoglobin with a mass fraction of 1% (the percentage relative to the total mass of dry matter of oxidized starch and pullulan) to the composite gelatinized solution obtained in step (2), and stir magnetically at 60°C for 1 hour to obtain an electrospinning solution.

[0064] (4) The electrospinning solution obtained in step (3) was electrospinned at an electrospinning voltage of 18kV, a spinning distance of 15cm, and a spinning solution driving speed of 1mL / h to prepare an oxidized starch / pullulan polysaccharide / bovine hemoglobin nanofiber membrane.

[0065] (5) Place the bio-based nanofiber membrane obtained in step (4) into a sealed container filled with ethylene gas and adsorb it at room temperature and pressure for 12 hours.

[0066] Comparative Example 1

[0067] Following steps (2) and (4) of Example 1, starch / pullulan nanofiber membranes were prepared by electrospinning using unoxidized starch (cassava starch) and pullulan as raw materials, and the differences in electrospinning between starch / pullulan and oxidized starch / pullulan were observed.

[0068] Comparative Example 2

[0069] Following steps (1)(2)(4)(5) of Example 1, nanofiber membranes were prepared by electrospinning using oxidized starch / pullulan polysaccharide solution as raw material, and the ethylene adsorption capacity was measured.

[0070] Tests showed that the obtained oxidized starch / pullulan nanofiber membrane did not have ethylene adsorption capacity.

[0071] Comparative Example 3

[0072] Take soy protein isolate, silk protein, rice protein, and bovine hemoglobin powder, and use untreated dry protein powder as adsorbent material according to step (5) of Example 1, and determine the ethylene adsorption capacity at room temperature and pressure.

[0073] Comparative Example 4

[0074] According to steps (2), (3), and (4) of Example 1, pullulan polysaccharide, soy protein isolate, silk protein, rice protein, and bovine hemoglobin powder were used as raw materials (the mass ratio of protein to pullulan polysaccharide was 1%). Pullulan polysaccharide-protein nanofiber membranes were prepared by electrospinning. According to step (5) of Example 1, pullulan polysaccharide-protein nanofiber membranes were used as adsorbent materials, and the ethylene adsorption capacity under normal temperature and pressure was measured.

[0075] like Figure 1 As shown, using an aqueous solution of oxidized starch, pullulan, and protein as the electrospinning solution, under appropriate electrospinning conditions, nanofiber membranes with uniform fiber diameter, good continuity, and no beading can be obtained. In contrast, the starch-pullulan mixture in Comparative Example 1 hardly formed Taylor cones during electrospinning, and many droplets appeared on the receiving plate (marked with red circles), with an average droplet count of 235, without fiber deposition. This indicates that oxidized starch-pullulan has excellent electrospinning properties, while native starch-pullulan does not possess this property, which may be related to the strong molecular entanglement of the oxidized starch and pullulan mixture solution.

[0076] After testing, such as Figure 2 As shown (where ethylene adsorption capacity is based on the mass of the adsorbent material), different protein powders all possess a certain ethylene adsorption capacity. However, under the same conditions, the ethylene adsorption capacity of protein powders is significantly lower than that of oxidized starch-pullulan-protein nanofiber membranes. Furthermore, the pure pullulan-protein nanofiber membrane exhibits a uniform fiber structure, and the ethylene adsorption capacity of the polysaccharide nanofiber membrane with the same protein content is slightly lower than that of the oxidized starch-polysaccharide-protein nanofiber membrane. It is believed that the addition of oxidized starch not only saves on raw material costs but also improves protein dispersibility, which facilitates the adsorption of ethylene by the fiber membrane.

[0077] Compared with the ethylene adsorption effect of the oxidized starch / pullulan nanofiber membrane in Comparative Example 2, it can be seen that the main component responsible for ethylene adsorption in the bio-based nanofiber membrane is protein. Compared with the ethylene adsorption effect of protein powder in Comparative Example 3, the bio-based nanofiber membrane exhibits a higher ethylene adsorption capacity, reaching a maximum of 15.4 cm⁻¹. 3 / g indicates that increasing the specific surface area of ​​the protein is beneficial to increasing the contact area between the material and the gas, thereby increasing the ethylene adsorption capacity; the above results show that the oxidized starch-pullulan polysaccharide-protein nanofiber system is a potential ethylene adsorbent that can reduce production costs and has the potential to preserve fruits and vegetables.

[0078] Depend on Figure 3It can be seen that in the preservation experiment using bananas as the subject, the blank control group began to show small areas of browning and rotting on day 1, while Examples 1, 2, 3, and 4 showed no change. The effect was most obvious on day 4. On day 8, the blank control group and Example 1 showed complete browning and rotting, and the bananas became soft. Examples 1 and 4 still maintained a good condition, while Examples 2 and 3 showed different degrees of browning. The preservation effect corresponds to the ethylene adsorption results of the nanofiber membrane. Therefore, it can be seen that the bio-based nanofiber membrane provided by the present invention has a good preservation effect. The preparation method of the bio-based nanofiber membrane with ethylene adsorption properties provided by the present invention is simple, requires no chemical reagents, and has the characteristics of being environmentally friendly, green, and efficient.

[0079] It should be noted that, for those skilled in the art, the implementation of this invention is not limited to the above embodiments. Any changes, modifications, substitutions, combinations, or simplifications made without departing from the spirit and principle of this invention should be considered equivalent substitutions and are included within the protection scope of this invention.

Claims

1. A method for preparing a bio-based nanofibrous membrane, characterized by, The method comprises the following steps: (1) dispersing oxidized starch and pullulan in water to prepare an oxidized starch / pullulan mixed solution, and gelatinizing to obtain a starch-polymer complex gelatinized solution; wherein the carboxyl content of the oxidized starch is 0.08%-0.64%; the mass ratio of the oxidized starch to the pullulan in the oxidized starch / pullulan mixed solution is 3:1-1:3; (2) adding a water-soluble protein to the starch-polymer complex gelatinized solution obtained in step (1) and mixing by heating and stirring to obtain an electrospinning solution; wherein the mass of the water-soluble protein is 0.5-3% of the total mass of the oxidized starch and the pullulan; and (3) electrospinning the electrospinning solution obtained in step (2) to obtain a bio-based nanofiber membrane; wherein the electrospinning is performed under the following conditions: a voltage of 12-24 kV, a receiving distance of 5-25 cm, and a pushing speed of 0.5-2.5 mL / h.

2. The production method according to claim 1, characterized by, In step (1), the oxidized starch is prepared by using hydrogen peroxide and / or sodium hypochlorite as an oxidizing agent and copper sulfate as a catalyst to oxidize starch.

3. The production method according to claim 2, characterized by, The carboxyl content of the oxidized starch is 0.35%-0.45%; the starch is at least one of corn starch, potato starch and tapioca starch; the mass ratio of the copper sulfate to the starch is 0.01-0.1%; the hydrogen peroxide and / or sodium hypochlorite accounts for 24.75-33% of the mass of the starch; the oxidation treatment is performed at a temperature of 30-50 ℃ for 2-4 h.

4. The production method according to claim 1, characterized by, In step (1), the gelatinization is performed in a boiling water bath for 0.5-1.5 h.

5. The preparation method according to claim 1, characterized in that, In step (2), the water-soluble protein is one or more of soy protein isolate, silk fibroin, bovine hemoglobin and rice protein.

6. The method of claim 1, wherein, In step (2), the heating and stirring are performed at a temperature of 50-60 ℃.

7. The preparation method according to claim 1, characterized in that, In step (3), the electrospinning is performed at an ambient temperature of 20-35 ℃ and an ambient humidity of 25%-40%.

8. The bio-based nanofiber membrane prepared by the method of claim 1.

9. The bio-based nanofiber membrane of claim 8 for use in ethylene adsorption.

10. The bio-based nanofiber membrane of claim 8 for use in fruit preservation.

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