CN113969464A - Method for preparing novel zein nanofiber membrane by electrostatic spinning - Google Patents

Method for preparing novel zein nanofiber membrane by electrostatic spinning Download PDF

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Publication number
CN113969464A
CN113969464A CN202111348258.7A CN202111348258A CN113969464A CN 113969464 A CN113969464 A CN 113969464A CN 202111348258 A CN202111348258 A CN 202111348258A CN 113969464 A CN113969464 A CN 113969464A
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zein
electrostatic spinning
nanofiber membrane
novel
preparing
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范鑫
荣令爽
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Shaanxi University of Science and Technology
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Shaanxi University of Science and Technology
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    • DTEXTILES; PAPER
    • D04BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04HMAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/70Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
    • D04H1/72Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
    • D04H1/728Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K47/00Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
    • A61K47/30Macromolecular organic or inorganic compounds, e.g. inorganic polyphosphates
    • A61K47/42Proteins; Polypeptides; Degradation products thereof; Derivatives thereof, e.g. albumin, gelatin or zein
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K9/00Medicinal preparations characterised by special physical form
    • A61K9/70Web, sheet or filament bases ; Films; Fibres of the matrix type containing drug
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D67/00Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0002Organic membrane manufacture
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D71/00Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06Organic material
    • B01D71/74Natural macromolecular material or derivatives thereof
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01DMECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00Formation of filaments, threads, or the like
    • D01D5/0007Electro-spinning
    • D01D5/0015Electro-spinning characterised by the initial state of the material
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01DMECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00Formation of filaments, threads, or the like
    • D01D5/0007Electro-spinning
    • D01D5/0061Electro-spinning characterised by the electro-spinning apparatus
    • D01D5/0069Electro-spinning characterised by the electro-spinning apparatus characterised by the spinning section, e.g. capillary tube, protrusion or pin
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01DMECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00Formation of filaments, threads, or the like
    • D01D5/0007Electro-spinning
    • D01D5/0061Electro-spinning characterised by the electro-spinning apparatus
    • D01D5/0076Electro-spinning characterised by the electro-spinning apparatus characterised by the collecting device, e.g. drum, wheel, endless belt, plate or grid

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  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Public Health (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Pharmacology & Pharmacy (AREA)
  • Veterinary Medicine (AREA)
  • Medicinal Chemistry (AREA)
  • Epidemiology (AREA)
  • Inorganic Chemistry (AREA)
  • Bioinformatics & Cheminformatics (AREA)
  • Manufacturing & Machinery (AREA)
  • Proteomics, Peptides & Aminoacids (AREA)
  • Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
  • Artificial Filaments (AREA)

Abstract

The invention discloses a method for preparing a novel Zein nanofiber membrane by electrostatic spinning, which comprises the steps of dissolving Zein (Zein) powder in a mixed solution, and carrying out electrostatic spinning to prepare loose banded Zein nanofibers; the ratio of the zein to the mixed solvent is 11-15: 50 in terms of g: mL; the mixed solution is composed of a solution of acetone, n-butanol, ethanol and water in a mass ratio of 1.5-2: 0.5-1: 1.5-2: 0.5-1. According to the method for preparing the novel Zein nanofiber membrane through electrostatic spinning, provided by the invention, only Zein is used as a raw material, and the obtained Zein nanofiber has the advantages of good biocompatibility, good degradability and the like, and also contains a large number of active functional groups. The nano-fiber has the structural characteristics of nano-materials and the chemical characteristics of protein, and has wide development prospects in the fields of food industry (fruit preservation), drug delivery, air filtration and the like.

Description

Method for preparing novel zein nanofiber membrane by electrostatic spinning
Technical Field
The invention belongs to the technical field of high polymer materials, and relates to a method for preparing a novel zein nanofiber membrane by electrostatic spinning.
Background
The nanofiber refers to an ultra-fine fiber having a fiber diameter of less than 1000nm, and is widely used in the fields of biomedical materials, tissue engineering materials, air filter materials, food packaging materials, and the like because of its high specific surface area. The nanofibers can be prepared by templating, phase separation, self-assembly, electrospinning, and the like. Compared with other methods, the electrostatic spinning method has the advantages of simple production equipment, controllable process, low cost and the like. Currently, polymer materials used in electrospinning include synthetic polymers, natural polymers, and mixtures thereof. Compared with synthetic high polymers, natural high polymers have the advantages of wide sources, low cost, good biocompatibility, biodegradability and the like, and protein is increasingly concerned as one of the natural high polymers.
Zein (Zein) is a prolamin which has a unique amino acid composition, is rich in hydrophobic amino acids and is connected with each other by disulfide bonds and hydrophobic bonds. Zein can be used in food, medicine, cosmetic, chemical industry, etc., and can be used as sustained release agent for medicament to protect active ingredients of the medicament and make the medicament slowly release during drug property after being ingested by patients. Zein can be modified to prepare an adhesive to replace an artificial adhesive with serious pollution. The lack of the nonpolar amino acid hydrophobic amino acid and the alkaline and acidic amino acid in the zein structure at a high proportion determines the dissolution behavior of the zein, and simultaneously contains more sulfur-containing amino acids, so that the zein has strong lipophilicity and solubility, can be dissolved in an alcoholic solution with a certain concentration, has good film forming property, and has wide application prospect as a biodegradable material.
CN102587036A discloses a preparation method of nanofiber membrane which can be cultured by cell. The zein/polyvinyl alcohol nanofiber membrane is a cell culture carrier material, and the material comprises biodegradable natural high-molecular zein and biocompatible high-molecular polymer polyvinyl alcohol. The zein/polyvinyl alcohol nano ribbon fibers have the transverse dimension of 625-3920 nanometers, and the nano fibers are randomly stacked to form a nano fiber film. However, the zein is used as a base material, and other polymers are not added, so that the self-curling loose strip-shaped nanofiber membrane can be prepared, and the related research is not found in the existing reports.
The electrostatic spinning nanofiber has high specific surface area, and the protein has the advantages of good biocompatibility, good degradability and the like, and also contains a large amount of active functional groups; therefore, the electrostatic spinning protein-based nanofiber has the structural characteristics of the nanofiber and the chemical characteristics of protein, and has a good application prospect. The invention provides a method for preparing a novel zein nanofiber membrane by electrostatic spinning, and obtains a loose strip-shaped nanofiber membrane with high specific surface area and porosity compared with a traditional rodlike fiber membrane by utilizing the characteristics of good biocompatibility and degradability of zein.
Disclosure of Invention
The invention aims to solve the problems of small surface area, low porosity and insufficient stability of the existing rod-shaped nanofiber membrane.
Based on the purposes, the invention provides the method for preparing the novel zein nanofiber membrane by electrostatic spinning, and the method has the advantages of simple production equipment, mild action condition and low cost; the nanofiber membrane prepared by the method is in a curly loose band shape and has the structural characteristics of nanofibers and the chemical characteristics of protein.
In one aspect, the present invention relates to a method for preparing a novel zein nanofiber membrane by electrospinning, comprising the steps of: adding Zein (Zein) into the mixed solvent, heating and stirring at constant temperature until the Zein is completely dissolved to obtain Zein electrospinning solution; carrying out electrostatic spinning on Zein electrospinning solution to obtain a loose banded Zein nanofiber membrane; the ratio of the zein to the mixed solvent is 11-15: 50 in terms of g: mL.
Further, in the method for preparing the novel zein nanofiber membrane by electrostatic spinning, the mixed solvent is a solution with the mass ratio of acetone to n-butyl alcohol to ethanol to water being 1.5-2: 0.5-1: 1.5-2: 0.5-1.
Further, in the method for preparing the novel zein nanofiber membrane by electrostatic spinning, a 10mL syringe is used as an electrospinning liquid storage device in electrostatic spinning, a 21G stainless steel needle is used as an injection needle, the flow rate of the electrospinning liquid is controlled by a micro-injection pump, and a flat plate is used for receiving fibers.
Further, in the method for preparing the novel zein nanofiber membrane by electrostatic spinning, the electrostatic spinning process parameters comprise that the advancing speed is 0.5-4 mL/h, the voltage is 10-22 kV, the distance from a needle head to a receiving device is 8-20 cm, and the spinning time is 0.1-2 h.
On the other hand, the invention also provides an application of the novel zein nanofiber membrane prepared by preparing the novel zein nanofiber membrane through electrostatic spinning, which comprises a food storage material, a drug carrying material and an air filtering material.
Compared with the prior art, the invention has the following beneficial effects or advantages:
(1) the novel zein nanofiber membrane prepared by electrostatic spinning only takes zein as a raw material, and the obtained nanofiber membrane is in a curled loose strip shape, has the structural characteristics of a nanomaterial and the chemical characteristics of protein, and has excellent material performance;
(2) the preparation process of the novel zein nanofiber membrane prepared by electrostatic spinning is simple, the preparation cost is low, and the controllability is good;
(3) the novel zein nanofiber membrane prepared by electrostatic spinning provided by the invention takes natural high polymer as a base material, is green, environment-friendly, safe, reliable and good in degradability, and has wide development prospects in the fields of food industry (fruit preservation), drug delivery, air filtration and the like.
Drawings
FIG. 1 is a scanning electron microscope image of a Zein nanofiber membrane prepared from a Zein solution with the mass fraction of 20 wt%;
FIG. 2 is a scanning electron microscope image of a Zein nanofiber membrane prepared from a Zein solution with the mass fraction of 22wt percent (Zein).
FIG. 3 is a scanning electron microscope image of a Zein nanofiber membrane prepared from a Zein solution with the mass fraction of 25wt percent (Zein).
FIG. 4 is a scanning electron microscope image of a Zein nanofiber membrane prepared from a Zein (Zein) solution with the mass fraction of 30 wt%.
Detailed Description
The following examples are given to illustrate the technical aspects of the present invention, but the present invention is not limited to the following examples.
Example 1
This example provides the preparation process and scanning electron microscope results of a Zein nanofiber membrane prepared from a 20 wt% Zein (Zein) solution.
Weighing 20mL of a mixed solvent with the mass ratio of acetone, n-butanol, ethanol and water being 2:1:2:1, weighing 4g of Zein powder, adding the Zein powder into a beaker filled with the mixed solvent, adding a magnetic rotor, placing the beaker into a magnetic stirrer, heating to 80 ℃, stirring for 0.5h, taking out the beaker, standing at room temperature and cooling to obtain a Zein solution with the mass fraction of 20 wt%.
Adding a Zein solution with the mass fraction of 20 wt% into a 10mL screw injector by taking the Zein solution as an electrospinning solution, mounting the injector on a micro-injection pump, and setting electrostatic spinning process parameters: the advancing speed is 2mL/h, the voltage is 16kV, the distance from the needle head to the receiving device is 12cm, and the spinning time is 20 min; and then starting an electrostatic spinning experiment to obtain the loose banded Zein nanofiber membrane.
The test result shows that the fibers obtained by electrostatic spinning of the Zein solution with the mass fraction of 20 wt% are unstable, and the fibers have a fracture phenomenon, which is shown in a test picture of a scanning electron microscope (figure 1).
Example 2
The embodiment provides a preparation process and a scanning electron microscope result of a Zein nanofiber membrane prepared from a 22-30 wt% Zein (Zein) solution.
(1)22 wt% Zein (Zein) nanofiber membrane
Weighing 20mL of a mixed solvent with the mass ratio of acetone, n-butanol, ethanol and water being 3:1:3:1, weighing 4.4g of Zein powder, adding the Zein powder into a beaker filled with the mixed solvent, adding a magnetic rotor, placing the beaker into a magnetic stirrer, heating to 80 ℃, stirring for 0.5h, taking out the beaker, standing at room temperature and cooling to obtain a Zein solution with the mass fraction of 22 wt%.
Adding a Zein solution with the mass fraction of 22 wt% into a 10mL screw injector by taking the Zein solution as an electrospinning solution, mounting the injector on a micro-injection pump, and setting electrostatic spinning process parameters: the advancing speed is 0.5mL/h, the voltage is 10kV, the distance from the needle head to the receiving device is 8cm, and the spinning time is 6 min; and then starting an electrostatic spinning experiment to obtain the loose banded Zein nanofiber membrane.
(2)25 wt% Zein (Zein) nanofiber membrane
Weighing 20mL of a mixed solvent with the mass ratio of acetone, n-butanol, ethanol and water being 2:1:2:1, weighing 5g of Zein powder, adding the Zein powder into a beaker filled with the mixed solvent, adding a magnetic rotor, placing the beaker into a magnetic stirrer, heating to 80 ℃, stirring for 0.5h, taking out the beaker, standing at room temperature and cooling to obtain a Zein solution with the mass fraction of 25 wt%.
Adding a Zein solution with the mass fraction of 25 wt% into a 10mL screw injector by taking the Zein solution as an electrospinning solution, mounting the injector on a micro-injection pump, and setting electrostatic spinning process parameters: the advancing speed is 2mL/h, the voltage is 16kV, the distance from the needle head to the receiving device is 12cm, and the spinning time is 20 min; and then starting an electrostatic spinning experiment to obtain the loose banded Zein nanofiber membrane.
(3)30 wt% Zein (Zein) nanofiber membrane
Weighing 20mL of a mixed solvent with the mass ratio of acetone, n-butanol, ethanol and water being 2:1:2:1, weighing 6g of Zein powder, adding the Zein powder into a beaker filled with the mixed solvent, adding a magnetic rotor, placing the beaker into a magnetic stirrer, heating to 80 ℃, stirring for 0.5h, taking out the beaker, standing at room temperature and cooling to obtain a Zein solution with the mass fraction of 30 wt%.
Adding a Zein solution with the mass fraction of 30 wt% into a 10mL screw injector by taking the Zein solution as an electrospinning solution, mounting the injector on a micro-injection pump, and setting electrostatic spinning process parameters: the advancing speed is 4mL/h, the voltage is 22kV, the distance from the needle head to the receiving device is 20cm, and the spinning time is 120 min; and then starting an electrostatic spinning experiment to obtain the loose banded Zein nanofiber membrane.
The test result shows that the fiber obtained by electrostatic spinning of the Zein solution with the mass fraction of 22-30 wt% is uniform and stable in thickness, wherein the electrostatic spinning fiber prepared from the Zein solution with the mass fraction of 22 wt% is shown in a scanning electron microscope test chart (figure 2), the electrostatic spinning fiber prepared from the Zein solution with the mass fraction of 25 wt% is shown in a scanning electron microscope test chart (figure 3), and the electrostatic spinning fiber prepared from the Zein solution with the mass fraction of 30 wt% is shown in a scanning electron microscope test chart (figure 4).
At present, most of base materials commonly used for preparing nano fibers by utilizing electrostatic spinning are synthetic high polymers (polyacrylonitrile, polyvinylpyrrolidone, polyvinyl alcohol and the like), but the base materials have the problems of difficult degradation or easy secondary pollution after degradation and the like although the base materials have good stability. The partially synthesized high polymer has certain toxicity and is not suitable for application in the fields of food industry, drug delivery and the like. Therefore, the invention takes natural high polymer (zein) as a base material: the environment-friendly, safe and reliable and good in degradability, and can avoid the problems.
In conclusion, the invention provides a method for preparing a novel Zein nanofiber membrane by electrostatic spinning, the preparation method is simple and effective, the conditions are mild, and Zein has the advantages of good biocompatibility, good degradability and the like and also contains a large amount of active functional groups; therefore, the nano-fiber has the structural characteristics of nano-materials and the chemical characteristics of protein, and has wide development prospect in the fields of food industry (fruit preservation), drug delivery, air filtration and the like.
As described above, the present invention can be preferably implemented, and the above-mentioned embodiments only describe the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various changes and modifications of the technical solution of the present invention made by those skilled in the art without departing from the design spirit of the present invention shall fall within the protection scope defined by the present invention.

Claims (8)

1. A method for preparing a novel zein nanofiber membrane by electrostatic spinning, which comprises the following steps: adding Zein (Zein) into the mixed solvent, heating and stirring at constant temperature until the Zein is completely dissolved to obtain Zein electrospinning solution; carrying out electrostatic spinning on Zein electrospinning solution to obtain a loose banded Zein nanofiber membrane; the ratio of the zein to the mixed solvent is 11-15: 50 in terms of g: mL.
2. The method for preparing the novel zein nanofiber membrane through electrostatic spinning according to claim 1, wherein the mixed solvent is a solution prepared from acetone, n-butanol, ethanol and water in a mass ratio of 1.5-2: 0.5-1: 1.5-2: 0.5-1.
3. The method for preparing the novel zein nanofiber membrane by electrostatic spinning according to claim 1, wherein a 10mL syringe is used as an electrospinning liquid storage device in the electrostatic spinning, a stainless steel needle with the specification of 21G is used as an injection needle, the flow rate of the electrospinning liquid is controlled by a micro-injection pump, and a flat plate is used for receiving the fibers.
4. The method for preparing the novel zein nanofiber membrane by electrostatic spinning according to claim 1, wherein the electrostatic spinning process parameters comprise a propelling speed of 0.5-4 mL/h, a voltage of 10-22 kV, a distance from a needle to a receiving device of 8-20 cm, and a spinning time of 0.1-2 h.
5. A nanofiber membrane prepared by the method as claimed in any one of claims 1 to 4.
6. Use of the nanofiber membrane of claim 5 in food storage materials.
7. Use of the nanofiber membrane of claim 5 in a drug delivery material.
8. Use of the nanofibrous membrane of claim 5 in an air filter material.
CN202111348258.7A 2021-11-15 2021-11-15 Method for preparing novel zein nanofiber membrane by electrostatic spinning Pending CN113969464A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115517360A (en) * 2022-09-30 2022-12-27 陕西科技大学 Plant-based meat analogue and preparation method thereof
CN117188038A (en) * 2023-09-06 2023-12-08 西藏自治区农牧科学院农产品开发与食品科学研究所 Alcohol soluble protein nanofiber membrane and preparation method thereof
CN117802697A (en) * 2024-03-01 2024-04-02 中国农业大学 Method for improving mechanical strength of zein nanofiber membrane

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CN105088538A (en) * 2014-05-16 2015-11-25 深圳海东华科技有限公司 A preparation method of hydrophobic/super-hydrophobic protein coatings
US10640888B1 (en) * 2019-07-02 2020-05-05 University of Central Oklahoma Method and apparatus for accumulating cross-aligned fiber in an electrospinning device

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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
CN105088538A (en) * 2014-05-16 2015-11-25 深圳海东华科技有限公司 A preparation method of hydrophobic/super-hydrophobic protein coatings
US10640888B1 (en) * 2019-07-02 2020-05-05 University of Central Oklahoma Method and apparatus for accumulating cross-aligned fiber in an electrospinning device

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115517360A (en) * 2022-09-30 2022-12-27 陕西科技大学 Plant-based meat analogue and preparation method thereof
CN115517360B (en) * 2022-09-30 2024-02-23 陕西科技大学 Plant-based artificial meat and preparation method thereof
CN117188038A (en) * 2023-09-06 2023-12-08 西藏自治区农牧科学院农产品开发与食品科学研究所 Alcohol soluble protein nanofiber membrane and preparation method thereof
CN117802697A (en) * 2024-03-01 2024-04-02 中国农业大学 Method for improving mechanical strength of zein nanofiber membrane
CN117802697B (en) * 2024-03-01 2024-05-28 中国农业大学 Method for improving mechanical strength of zein nanofiber membrane

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