CN117802697A - Method for improving mechanical strength of zein nanofiber membrane - Google Patents

Method for improving mechanical strength of zein nanofiber membrane Download PDF

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Publication number
CN117802697A
CN117802697A CN202410233670.1A CN202410233670A CN117802697A CN 117802697 A CN117802697 A CN 117802697A CN 202410233670 A CN202410233670 A CN 202410233670A CN 117802697 A CN117802697 A CN 117802697A
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zein
nanofiber membrane
millet
nanofiber
membrane
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陈冲
王淑敏
陈娟
陈翰
王鹏杰
张伟博
任发政
胡瑶
朱银华
刘思源
王然
刘蓉
方冰
王晓玉
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China Agricultural University
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China Agricultural University
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    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02WCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W90/00Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
    • Y02W90/10Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics

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Abstract

The invention provides a method for improving mechanical strength of zein nanofiber membrane, which comprises the steps of uniformly mixing zein, millet zein and a solvent to obtain a mixed solution; uniformly mixing the mixed solution with a cationic surfactant to obtain spinning solution; and carrying out electrostatic spinning on the spinning solution to obtain the composite nanofiber membrane. According to the method for improving the mechanical strength of the zein nanofiber membrane, the zein and the zein are blended, and the zein molecular chains are entangled, so that the obtained composite nanofiber membrane has a more compact structure, the mechanical properties of the zein nanofiber membrane are effectively improved, the tensile strength, the elongation at break and the Young modulus are remarkably improved, and meanwhile, the water stability of the composite nanofiber membrane is also improved.

Description

Method for improving mechanical strength of zein nanofiber membrane
Technical Field
The invention belongs to the field of nanofiber membranes, and particularly relates to a method for improving mechanical strength of a zein nanofiber membrane.
Background
Due to good film forming, biocompatibility and biodegradability, more and more researchers are beginning to work on the production of zein (zein) electrospun fiber films encapsulating antibacterial substances for food preservation. However, unlike synthetic polymers, which have the characteristic of maintaining high stability for a long period of time, bio-based polymer electrospun fiber membranes have poor mechanical strength. Although zein has higher heat resistance, inherent hydrophobicity, and numerous modifiable groups compared to other hydrophilic proteins and carbohydrate-based polymeric materials, the zein nanofiber membranes have relatively excellent mechanical properties. However, the mechanical strength of the zein electrospun fiber membranes currently available is still not ideal, and therefore, it is necessary to increase the mechanical strength of zein nanofiber membranes.
On the one hand, crosslinking is a common method for improving the mechanical properties of bio-based polymer nanofiber membranes, and previous studies have demonstrated that physical, chemical and enzymatic crosslinking methods can improve the mechanical properties of Gao Shengwu-based polymer nanofiber membranes. Physical crosslinking, while safe and more acceptable to consumers, is less crosslinking because crosslinking generally occurs only on the surface of the material; furthermore, the physical crosslinking process may impair the properties of the fibers and is not suitable for treating fiber materials loaded with unstable active ingredients. Although chemical crosslinking can effectively improve the mechanical properties of the fiber material, the chemical crosslinking agent used generally has certain toxicity and possibly remains on the surface of the fiber membrane, thus having potential safety hazards. The enzyme crosslinking treatment has the characteristics of mild and safe, but the reaction conditions are often required to be strictly controlled, and the cost is high.
On the other hand, hybrid electrospinning is increasingly being used to enhance the mechanical strength of nanofiber materials due to the features of simplicity, safety, etc., where the choice of polymer blend is critical. The published researches mostly mix various synthetic polymers for co-electrospinning, but the use of the synthetic polymers can cause serious harm to human health and natural environment, and is not suitable for food industry application. In addition, degradable synthetic polymers such as polyglycolic acid, polylactic acid, polycaprolactone, etc. are blended with natural bio-based polymers to prepare electrospun fiber membranes, which, although they can significantly improve water stability, generally reduce the bioactivity of natural bio-based polymers and the solvents used tend to be expensive and toxic. Therefore, the development of new bio-based polymers for preparing composite fiber materials is significant for widening the application of bio-based nanofiber materials in product packaging.
Disclosure of Invention
In view of the above, the present invention aims to provide a method for improving mechanical strength of zein nanofiber membrane, so as to increase compactness of zein nanofiber membrane structure by adding zein, and effectively improve mechanical properties of zein nanofiber membrane.
In order to achieve the above purpose, the technical scheme of the invention is realized as follows:
in a first aspect, the present invention provides a method for improving the mechanical strength of zein nanofiber membranes comprising the steps of:
uniformly mixing zein, millet zein and a solvent to obtain a mixed solution;
uniformly mixing the mixed solution with a cationic surfactant to obtain spinning solution;
and carrying out electrostatic spinning on the spinning solution to obtain the composite nanofiber membrane.
Further, the mass ratio of zein to millet prolamin is 1:0.5-2, for example, 2:1, 1:1, 1:1.5, 1:2.
Further, the sum of the mass concentration of zein and the mass concentration of the millet prolamin in the mixed solution is 25% -40%, such as 25%, 30%, 35% and 40%.
Further, the cationic surfactant is added in an amount of 1% -10% by mass of zein, for example, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%.
Further, the cationic surfactant is TEBAC.
Further, the solvent is an organic acid; the organic acid is preferably acetic acid.
Further, the extraction method of the millet prolamin comprises the following steps:
crushing millet into millet powder, uniformly mixing the millet powder with water, homogenizing by a colloid mill, and centrifuging to obtain a precipitate;
mixing the precipitate with ethanol, centrifuging, adding sodium chloride solution into supernatant, centrifuging, washing the precipitate with water, and lyophilizing to obtain millet prolamin.
Further, the electrospinning conditions were:
the flow rate is 0.5-3 mL/h, the voltage is 16-24 and kv, the receiving distance is 8-12 cm, and the rotating speed of the roller is 200-1500 rpm.
In a second aspect, the present invention provides a nanofiber membrane made according to the above method.
In a third aspect, the present invention provides a nanofiber membrane made according to the above method or the use of a nanofiber membrane according to the above in packaging of a product, preferably a fruit or vegetable.
In a fourth aspect, the present invention provides the use of a zein protein to improve the performance of a zein nanofiber membrane, wherein the use comprises at least one of the following:
(1) The application of the zein nanofiber membrane in increasing the tensile strength of the zein nanofiber membrane;
(2) The application of the zein nanofiber membrane in increasing the breaking elongation of the zein nanofiber membrane;
(3) Use in increasing young's modulus of zein nanofiber membranes;
(4) The application of the zein nanofiber membrane in improving the water stability of the zein nanofiber membrane.
Compared with the prior art, the method for improving the mechanical strength of the zein nanofiber membrane has the following advantages:
according to the method for improving the mechanical strength of the zein nanofiber membrane, the zein and the zein are mixed according to a specific proportion, and the zein molecular chains are entangled to enable the obtained composite nanofiber membrane to have a more compact structure, so that the mechanical property, tensile strength, elongation at break and Young modulus of the zein nanofiber membrane are effectively improved, and meanwhile, the water stability of the composite nanofiber membrane is also improved.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention. In the drawings:
FIG. 1 is a graph showing the volume change of the zein/MG composite nanofiber membrane of test example 3 after 24 hours of immersion in water;
FIG. 2 is a scanning electron microscope image of the zein/MG composite nanofiber membrane of test example 3 immersed in water for 24 hours;
FIG. 3 is a schematic view showing the formation process of zein fiber membrane (a) and zein/MG composite nanofiber membrane (b) in example 2.
Detailed Description
It should be noted that, without conflict, the embodiments of the present invention and features of the embodiments may be combined with each other.
The invention will be described in detail below with reference to the drawings in connection with embodiments.
The main reagents and test instruments used in the following examples are shown in tables 1 and 2.
TABLE 1 Main test reagents
TABLE 2 Main instrumentation
Example 1
The present embodiment provides a method for extracting millet prolamin (MG), comprising the steps of:
pulverizing semen Setariae granule into semen Setariae powder with pulverizer, mixing semen Setariae powder with water at ratio of 1:10, homogenizing with colloid mill for 15 min, centrifuging at 25deg.C and 3500×g for 10 min, removing supernatant, and collecting precipitate. The precipitate was stirred continuously with an 80% (v/v) ethanol solution at a ratio of 1:8 (w/v) at 37℃for 3 hours, and then centrifuged (10 min at 3500 Xg). Adding 3 times of cold sodium chloride solution into the obtained supernatant until the final concentration of sodium chloride is 0.3% (w/v), standing at 4deg.C for 24h, centrifuging, washing with water, precipitating, and freeze drying to obtain MG.
Example 2
The embodiment provides a method for improving mechanical strength of zein nanofiber membrane, wherein the mechanical strength of zein nanofiber membrane is improved by preparing a composite nanofiber membrane by co-electrospinning millet prolamin and zein, and the specific steps comprise:
(1) As shown in the formulation in Table 3, zein (zein) and zein (MG) were added using acetic acid as a solvent, and magnetically stirred overnight at 25℃to be sufficiently dissolved, thereby obtaining a mixed solution.
TABLE 3 formulation design of zein/MG composite nanofiber membranes
(2) Adding 2% (w/w, based on the sum of zein and MG mass) of a cationic surfactant TEBAC to the mixed solution, stirring at room temperature for 2 h to fully dissolve the TEBAC, and preparing the spinning solution.
(3) The spinning solution is kept stand for 10 min to remove bubbles, and then a certain amount of spinning solution is sucked into a 10 mL injector for electrostatic spinning. The spinning parameters are as follows: the voltage is 16kv, the receiving distance is 8cm, the rotating speed of the roller is 1000rpm, and the flow rate is 0.5 mL/h, thus obtaining the zein/MG composite nanofiber membrane.
As shown in Table 3, ZM-1/0, ZM-2/1, ZM-1/2 and ZM-0/1 are marked, respectively, according to the addition ratio of zein/MG. Wherein ZM-1/0 is a separate zein nanofiber membrane and ZM-0/1 is a separate MG nanofiber membrane.
Test example 1 morphological evaluation of zein/MG composite nanofiber membranes
Morphological evaluation was performed on the zein/MG composite nanofiber membrane prepared in example 2 using a scanning electron microscope. The results show that the fibers in the zein/MG composite nanofiber membrane are randomly oriented, smooth, uniform, and free of beads. No significant phase separation was observed, indicating good compatibility of the two components zein and MG. In addition, the average fiber diameters of ZM-1/0, ZM-2/1, ZM-1/2 and ZM-0/1 are in the range of 200-300 nm, 218.12 + -51.04 nm, 252.39 + -44.67 nm, 273.73 + -50.28 nm, 281.62 + -45.89 and 262.49 + -49.24 nm, respectively.
Test example 2 mechanical Properties of zein/MG composite nanofiber Membrane
In this test example, the composite nanofiber membrane of example 2 was cut into a size of 30 mm ×3× 3 mm, and the static mechanical properties of the composite nanofiber membrane were analyzed by a universal tester at a drawing speed of 1 mm/s. Five determinations were made for the zein/MG composite nanofiber membranes in different ratios, respectively.
Tensile Strength (TS), elongation at break (EB) and Young's Modulus (YM) were calculated as follows:
wherein,F m is the recorded maximum load (N),Sis the cross-sectional area of the sample,L b is the length (mm) at the break point,L 0 is the initial length of the sample and,L m is the test length (mm) corresponding to the maximum load.
The tensile strength, young's modulus and elongation at break of the composite nanofiber membranes of different proportions zein/MG are shown in Table 4. The MG fiber film alone (ZM-0/1) has higher tensile strength, elongation at break, and young's modulus than the zein nanofiber film alone (ZM-1/0). For the zein/MG composite nanofiber membrane, the overall mechanical properties are gradually increased along with the increase of the MG adding proportion. Wherein the mechanical strength of the composite fiber film ZM-1/2 is obviously higher than that of the individual zein nanofiber film and the individual MG nanofiber film, which shows that the MG can effectively improve the mechanical property of the zein nanofiber film.
TABLE 4 tensile Strength, elongation at break and Young's modulus of zein/MG composite nanofiber membranes
Test example 3 swelling Property of zein/MG composite nanofiber Membrane
To observe the morphology of the zein/MG composite nanofiber membrane after water absorption, the test example soaked the zein/millet prolamin composite nanofiber membrane samples of different proportions of example 2 in deionized water for 24h, and fig. 1 shows the volume change of the zein/MG composite nanofiber membrane samples of different proportions after soaking in deionized water for 24 h. It can be seen that composite nanofiber membranes of different zein/MG ratios have different swelling behavior after exposure to deionized water. As shown in FIG. 1, the volume of zein nanofiber membrane alone (ZM-1/0) was 28.82% of the initial volume upon initial exposure to deionized water; the volumes of the zein/MG composite nanofiber membranes ZM-2/1, ZM-1/1 and ZM-1/2 are 57.46%, 74.72% and 85.03% of the initial volumes respectively; whereas MG nanofiber membrane alone (ZM-0/1) swelled due to water absorption, the volume became 120.86% of the original volume. These results demonstrate that the addition of MG can reduce the extent of shrinkage of zein nanofiber membranes upon initial exposure to deionized water. As the exposure time to deionized water increased, all nanofiber membrane samples continued to shrink, resulting in a gradual decrease in volume. After 24. 24h infiltration in deionized water, the volumes of ZM-1/0, ZM-2/1, ZM-1/2 and ZM-0/1 were 12.57%, 19.97%, 22.27%, 28.46% and 34.69% of the initial volumes, respectively. These results indicate that when the average fiber diameter is the same, the shrinkage of the zein nanofiber membrane after initial exposure to deionized water is reduced as the MG addition ratio increases; however, when the immersion time in deionized water is long, the improvement effect is not remarkable.
Further, this test example uses a scanning electron microscope to observe the swelling behavior of the zein nanofiber membrane of example 2 after 24h of the zein/MG composite nanofiber membrane was immersed in deionized water (fig. 2). The results show that compared with the original fiber form, the zein nanofiber membrane (ZM-1/0) almost loses the original fiber structure after being soaked in deionized water for 0.5 h, and the fiber is adhered to form a film, so that only some pores formed by incompletely adhered fibers can be observed; and as the immersion time increases, the membrane dissolves to form large pores, indicating poor water stability of the zein nanofiber membrane. However, ZM-0/1 still better maintained the fiber structure after 24h wet in deionized water, only increased diameter and reduced inter-fiber voids were observed after fiber swelling. With the increase of the MG adding proportion, the water stability of the zein/MG composite nanofiber membrane is improved. Wherein, the ZM-1/2 composite nanofiber membrane can still maintain the fiber form after being soaked in deionized water for 24 and h, although the fiber absorbs water and swells, so that the inter-fiber pores are reduced.
Test example 4 molecular Structure of zein/MG composite nanofiber Membrane
This test example analyzes the intermolecular interactions between the functional groups and the components in the composite nanofiber membrane of example 2 in different proportions zein/MG by fourier transform infrared spectroscopy in ATR mode. The fiber film sample to be tested was placed on the ATR fitting, which was carefully pressed down to ensure good contact of the sample with the ATR crystals. Wavelength scan range of 400-4000 cm -1 Resolution of 4 cm -1 The spectra of each sample were collected after an average of 32 scans, with empty ATR crystals as reference.
Composite nanofiber membranes of different zein/MG ratios have similar infrared spectra. The IR spectrum is reported to be 1654 cm -1 The characteristic peaks at these correspond to the c=o stretching vibration, C-N stretching vibration and N-H bending vibration of the amide i band. The characteristic peak of zein nanofiber membrane (ZM-1/0) is at 1653 cm -1 In the zein/MG composite fiber film, the characteristic peak was blue-shifted (1654 cm) -1 ) And the peak intensity increases significantly, indicating a significant interaction between zein and MG. The characteristic maximum of ZM-1/0 in the amide I band occurs at 1653-1653 cm -1 Here, the characteristic maximum in the amide II band occurs at 1541 cm -1 Where it is located. And for zein/MG composite fiber membranes the characteristic maximum in the amide I band occurs at 1654 cm -1 This reflects, in the fibrous membrane, the changes in the alpha-helical structure and small amounts of random coil structure. Para-amide I band in 1700-1600 cm -1 Second derivative and gaussian curve fitting in the range the secondary structure content of the zein/MG composite fiber film was analyzed and the results are shown in table 5. As the MG addition ratio increases, the β -turn content gradually decreases, while the α -helix content gradually increases. It is known that fibrous membranes with high alpha-helix content generally have a more dense structure which results in zein/MG composite fibrous membranesHas higher mechanical strength.
MG has a molecular weight significantly less than zein, so that in acetic acid solvent, the MG molecular chains are more extended. As shown in fig. 3, in the electrospinning process, zein and MG molecular chains are continuously stretched by static electricity when a voltage is applied, thereby exposing more free amino groups and hydroxyl groups. Due to the similar structure and properties of zein and MG, good compatibility between them favors more adequate interactions between the molecular chains. Along with the electrostatic spinning process, the zein and MG molecular chains are continuously entangled, fused and stretched to finally form the composite nanofiber membrane. Good compatibility, sufficient interaction, a greater degree of molecular chain entanglement results in zein/MG composite fiber membranes having significantly higher mechanical strength than zein fiber membranes and MG fiber membranes alone.
TABLE 5 secondary Structure content of composite nanofiber membranes with different zein/MG ratios
Note that: the different lower case letters of each column represent significant differences.
In conclusion, the zein and the extracted millet prolamin (MG) are co-electrospun to prepare the composite nanofiber membrane, the swelling property, the surface hydrophilicity and the mechanical property of the zein/MG composite nanofiber membrane are measured, the formation mechanism of the zein/MG composite nanofiber membrane is explored, and the following conclusion is obtained:
1. the mechanical properties of the zein nanofiber membrane can be effectively improved by adding the MG. Wherein the mechanical strength of the composite nanofiber membrane ZM-1/2 is significantly higher than that of the zein nanofiber membrane and the MG nanofiber membrane alone.
2. The addition of MG increases entanglement between zein and MG molecular chains, so that the zein/MG composite nanofiber membrane forms a more compact structure.
3. Good compatibility, sufficient interaction, a greater degree of molecular chain entanglement results in a significant increase in the mechanical strength of the zein/MG composite fibre membrane.
4. The presence of MG may improve the stability of the zein nanofiber membrane upon initial exposure to deionized water, but the improvement is not significant when the exposure time is longer.

Claims (10)

1. A method for improving the mechanical strength of zein nanofiber membranes, comprising the steps of:
uniformly mixing zein, millet zein and a solvent to obtain a mixed solution;
uniformly mixing the mixed solution with a cationic surfactant to obtain spinning solution;
and carrying out electrostatic spinning on the spinning solution to obtain the composite nanofiber membrane.
2. The method according to claim 1, characterized in that: the mass ratio of the zein to the millet zein is 1:0.5-2.
3. The method according to claim 1, characterized in that: the sum of the mass concentration of zein and millet zein in the mixed solution is 25% -40%.
4. The method according to claim 1, characterized in that: the addition amount of the cationic surfactant is 1% -10% of the mass of zein.
5. The method according to claim 1, characterized in that: the cationic surfactant is TEBAC.
6. The method according to claim 1, characterized in that the extraction method of the prolamin from millet comprises the following steps:
crushing millet into millet powder, uniformly mixing the millet powder with water, homogenizing by a colloid mill, and centrifuging to obtain a precipitate;
mixing the precipitate with ethanol, centrifuging, adding sodium chloride solution into supernatant, centrifuging, washing the precipitate with water, and lyophilizing to obtain millet prolamin.
7. The method according to claim 1, characterized in that: the electrostatic spinning conditions are as follows:
the flow rate is 0.5-3 mL/h, the voltage is 16-24 and kv, the receiving distance is 8-12 cm, and the rotating speed of the roller is 200-1500 rpm.
8. A nanofiber membrane made according to the method of any one of claims 1-7.
9. Use of a nanofiber membrane made according to the method of any one of claims 1-7 or according to claim 8 in product packaging.
10. Use of a zein to improve zein nanofiber membrane performance, comprising at least one of the following:
(1) The application of the zein nanofiber membrane in increasing the tensile strength of the zein nanofiber membrane;
(2) The application of the zein nanofiber membrane in increasing the breaking elongation of the zein nanofiber membrane;
(3) Use in increasing young's modulus of zein nanofiber membranes;
(4) The application of the zein nanofiber membrane in improving the water stability of the zein nanofiber membrane.
CN202410233670.1A 2024-03-01 2024-03-01 Method for improving mechanical strength of zein nanofiber membrane Pending CN117802697A (en)

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Citations (8)

* Cited by examiner, † Cited by third party
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WO2012091087A1 (en) * 2010-12-29 2012-07-05 太陽化学株式会社 Functional material-containing mask
CN102587036A (en) * 2012-03-28 2012-07-18 吉林大学 Preparation method of corn alcohol-soluble protein nanofiber membrane used for cell culture
CN106048744A (en) * 2016-06-27 2016-10-26 天津工业大学 Method for preparing extracellular matrix-simulated nanometer fiber dressing through electrostatic spinning
CN109056083A (en) * 2018-08-30 2018-12-21 浙江工业大学 A kind of preparation method of the cinnamaldehyde oil liposome antibacterial duplicature of controllable release
CN111850837A (en) * 2020-07-24 2020-10-30 吉林农业大学 Zein-based uniaxial electrostatic spinning oriented fiber film and preparation method thereof
CN113897734A (en) * 2021-10-19 2022-01-07 北京工商大学 Zein/polyphenol/nano zinc oxide composite fiber film and preparation method thereof
CN113969464A (en) * 2021-11-15 2022-01-25 陕西科技大学 Method for preparing novel zein nanofiber membrane by electrostatic spinning
CN116240676A (en) * 2021-12-07 2023-06-09 广东海洋大学 Collagen/zein/gallic acid composite nanofiber antibacterial membrane and application thereof

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012091087A1 (en) * 2010-12-29 2012-07-05 太陽化学株式会社 Functional material-containing mask
CN102587036A (en) * 2012-03-28 2012-07-18 吉林大学 Preparation method of corn alcohol-soluble protein nanofiber membrane used for cell culture
CN106048744A (en) * 2016-06-27 2016-10-26 天津工业大学 Method for preparing extracellular matrix-simulated nanometer fiber dressing through electrostatic spinning
CN109056083A (en) * 2018-08-30 2018-12-21 浙江工业大学 A kind of preparation method of the cinnamaldehyde oil liposome antibacterial duplicature of controllable release
CN111850837A (en) * 2020-07-24 2020-10-30 吉林农业大学 Zein-based uniaxial electrostatic spinning oriented fiber film and preparation method thereof
CN113897734A (en) * 2021-10-19 2022-01-07 北京工商大学 Zein/polyphenol/nano zinc oxide composite fiber film and preparation method thereof
CN113969464A (en) * 2021-11-15 2022-01-25 陕西科技大学 Method for preparing novel zein nanofiber membrane by electrostatic spinning
CN116240676A (en) * 2021-12-07 2023-06-09 广东海洋大学 Collagen/zein/gallic acid composite nanofiber antibacterial membrane and application thereof

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