CN117488416A - Porous nano-carrier with adjustable morphology and aperture based on emulsion electrostatic spinning and preparation method thereof - Google Patents
Porous nano-carrier with adjustable morphology and aperture based on emulsion electrostatic spinning and preparation method thereof Download PDFInfo
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- 239000002539 nanocarrier Substances 0.000 title claims abstract description 71
- 238000010041 electrostatic spinning Methods 0.000 title claims abstract description 56
- 239000000839 emulsion Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 36
- 239000007762 w/o emulsion Substances 0.000 claims abstract description 40
- 238000000034 method Methods 0.000 claims abstract description 29
- 150000004676 glycans Chemical class 0.000 claims abstract description 9
- 229920001600 hydrophobic polymer Polymers 0.000 claims abstract description 9
- 229920001282 polysaccharide Polymers 0.000 claims abstract description 9
- 239000005017 polysaccharide Substances 0.000 claims abstract description 9
- 238000005516 engineering process Methods 0.000 claims abstract description 6
- 230000001804 emulsifying effect Effects 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 238000009987 spinning Methods 0.000 claims description 42
- 239000001856 Ethyl cellulose Substances 0.000 claims description 17
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 claims description 17
- 235000019325 ethyl cellulose Nutrition 0.000 claims description 17
- 229920001249 ethyl cellulose Polymers 0.000 claims description 17
- 239000001814 pectin Substances 0.000 claims description 12
- 235000010987 pectin Nutrition 0.000 claims description 12
- 229920001277 pectin Polymers 0.000 claims description 12
- FTSSQIKWUOOEGC-RULYVFMPSA-N fructooligosaccharide Chemical compound OC[C@H]1O[C@@](CO)(OC[C@@]2(OC[C@@]3(OC[C@@]4(OC[C@@]5(OC[C@@]6(OC[C@@]7(OC[C@@]8(OC[C@@]9(OC[C@@]%10(OC[C@@]%11(O[C@H]%12O[C@H](CO)[C@@H](O)[C@H](O)[C@H]%12O)O[C@H](CO)[C@@H](O)[C@@H]%11O)O[C@H](CO)[C@@H](O)[C@@H]%10O)O[C@H](CO)[C@@H](O)[C@@H]9O)O[C@H](CO)[C@@H](O)[C@@H]8O)O[C@H](CO)[C@@H](O)[C@@H]7O)O[C@H](CO)[C@@H](O)[C@@H]6O)O[C@H](CO)[C@@H](O)[C@@H]5O)O[C@H](CO)[C@@H](O)[C@@H]4O)O[C@H](CO)[C@@H](O)[C@@H]3O)O[C@H](CO)[C@@H](O)[C@@H]2O)[C@@H](O)[C@@H]1O FTSSQIKWUOOEGC-RULYVFMPSA-N 0.000 claims description 8
- 229940107187 fructooligosaccharide Drugs 0.000 claims description 8
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 5
- 238000004458 analytical method Methods 0.000 claims description 3
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 2
- 229920003141 Eudragit® S 100 Polymers 0.000 claims description 2
- 229920002301 cellulose acetate Polymers 0.000 claims description 2
- 238000001514 detection method Methods 0.000 claims description 2
- 235000011187 glycerol Nutrition 0.000 claims description 2
- 239000000661 sodium alginate Substances 0.000 claims description 2
- 235000010413 sodium alginate Nutrition 0.000 claims description 2
- 229940005550 sodium alginate Drugs 0.000 claims description 2
- 239000000203 mixture Substances 0.000 abstract description 4
- 238000001179 sorption measurement Methods 0.000 abstract description 4
- 230000001276 controlling effect Effects 0.000 abstract description 3
- 230000001105 regulatory effect Effects 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 39
- 239000000835 fiber Substances 0.000 description 23
- 239000002904 solvent Substances 0.000 description 22
- 239000011148 porous material Substances 0.000 description 19
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 11
- 238000011068 loading method Methods 0.000 description 9
- 238000001000 micrograph Methods 0.000 description 9
- 239000011259 mixed solution Substances 0.000 description 9
- 239000002121 nanofiber Substances 0.000 description 8
- 238000009210 therapy by ultrasound Methods 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000001523 electrospinning Methods 0.000 description 5
- 238000005191 phase separation Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical class OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000000265 homogenisation Methods 0.000 description 3
- 239000008204 material by function Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000010952 in-situ formation Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- 238000002145 thermally induced phase separation Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000007783 nanoporous material Substances 0.000 description 1
- 239000007764 o/w emulsion Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0015—Electro-spinning characterised by the initial state of the material
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- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Textile Engineering (AREA)
- Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
Abstract
The invention discloses a porous nano-carrier with adjustable morphology and aperture based on emulsion electrostatic spinning and a preparation method thereof. The preparation method comprises the following steps: (1) Taking a polysaccharide solution as a disperse phase and a hydrophobic polymer solution as a continuous phase; (2) Mixing the disperse phase solution and the continuous phase solution, homogenizing and emulsifying to obtain water-in-oil emulsion; (3) is prepared by an electrostatic spinning technology. According to the invention, the polysaccharide solution is used as a disperse phase, the hydrophobic polymer solution is used as a continuous phase for nano-carrier preparation, nano-carriers with different morphologies or different apertures can be simply constructed by regulating and controlling the composition of the solution and adding the regulator into the disperse phase, theoretical and method support is provided for controllable preparation of the porous nano-carrier, and a larger application space is promoted for application of the carrier in the aspects of adsorption, immobilization, sensors and the like.
Description
Technical Field
The invention relates to the technical field of functional materials, in particular to a porous nano-carrier with adjustable morphology and aperture based on emulsion electrostatic spinning and a preparation method thereof.
Background
Electrostatic spinning is a non-thermal processing technique for continuously preparing multi-scale, multi-structure carriers based on electrostatic forces. Modification of the morphology of electrospun fibers (e.g., the preparation of porous fibers) can further expand the range of applications. The porous material is a solid material with abundant microstructure, and is widely applied in the fields of adsorption separation, analysis, catalysis, energy storage, biology and the like due to the large specific surface area, low density, high porosity and adsorptivity. Methods for constructing porous nanofibers by means of electrospinning or post-treatment processes are mainly divided into three types.
(1) Thermally induced phase separation or vapor induced phase separation, as demonstrated by the Megelski study, the solution temperature decreases during volatilization of the solvent, and the decrease in temperature and increase in concentration together induce phase separation. In addition, the rapid volatilization of the solvent can lead to the sudden drop of the temperature of the micro-environment around the jet flow, the water vapor in the surrounding environment is condensed into tiny liquid drops on the surface of the jet flow, and holes are formed on the surface of the fiber after the liquid drops volatilize.
(2) The porous structure is obtained by a post-treatment mode of selectively dissolving the electrospun fiber component. In general, a blend of two polymers is prepared, and then one of the polymers is dissolved in a solvent-soaking post-treatment process to obtain a porous structure.
(3) The polymer electrospun fibers are swelled in a solvent and then subjected to solvent-induced crystallization to produce porous fibers, which are related to the solubility parameter, molecular weight and solvent immersion temperature of the polymer. In summary, in-situ formation of porous structures during electrospinning is difficult to accurately control the reproducibility of porous material preparation and the pore size and uniformity depending on the changes of spinning solution conditions and environmental conditions. The preparation of porous fiber based on electrostatic spinning post-treatment still has the defects of low preparation efficiency, only appearance of a pore structure on the surface layer of the fiber, incomplete removal of template polymer, large volume of dissipation solvent, need of additional drying process and the like. The method is characterized by simple process, controllable process and adjustable pore size, and has profound significance for expanding the application fields of electrostatic spinning technology and functional materials thereof.
In summary, in-situ formation of porous structures during electrospinning is difficult to accurately control the reproducibility of porous material preparation and the pore size and uniformity depending on the changes of spinning solution conditions and environmental conditions. The preparation of porous fiber based on electrostatic spinning post-treatment still has the defects of low preparation efficiency, only appearance of a pore structure on the surface layer of the fiber, incomplete removal of template polymer, large volume of dissipation solvent, need of additional drying process and the like. The method is characterized by simple process, controllable process and adjustable pore size, and has profound significance for expanding the application fields of electrostatic spinning technology and functional materials thereof.
Emulsion electrostatic spinning takes water-in-oil or oil-in-water emulsion as spinning fluid, and micro-nano fibers with complex structures (such as core-shell structures and co-continuous structures) can be prepared in one step through a single-shaft needle head device. In the electrostatic spinning process, dispersed phase solvent molecules need to migrate from the inside of the emulsion to the surface of the jet flow, so that volatilization is realized. In view of the immiscibility of the dispersed phase solvent and the continuous phase solvent, phase separation of the continuous phase solution occurs on the migration path of solvent molecules, which is an important theoretical basis for preparing porous nanofibers based on emulsion electrospinning. Studies have shown that increasing the amount of surfactant (emulsifier) added or increasing the humidity of the spinning environment can be used to eliminate or increase the porous structure of the fiber. Although the porous structure is easy to realize from nothing to nothing, the precise adjustment of the morphology and the pore structure of the nano-carrier based on the electrostatic spinning technology is not an efficient means.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide a porous nano-carrier with adjustable morphology and aperture based on emulsion electrostatic spinning and a preparation method thereof, so as to solve the problem of lacking a high-efficiency and accurate adjustment method for the morphology and pore structure of the nano-carrier.
The technical scheme for solving the technical problems is as follows:
the preparation method of the porous nano-carrier with adjustable morphology and aperture based on emulsion electrostatic spinning comprises the following steps:
(1) Preparing a polysaccharide solution as a disperse phase solution and a hydrophobic polymer solution as a continuous phase solution;
(2) Mixing the disperse phase solution obtained in the step (1) with the continuous phase solution, homogenizing and emulsifying to obtain water-in-oil emulsion;
(3) And (3) preparing the water-in-oil emulsion obtained in the step (2) through an electrostatic spinning technology.
Further, the polysaccharide in step (1) comprises at least one of pectin and sodium alginate; the hydrophobic polymer comprises at least one of ethylcellulose, cellulose acetate, eudragit S100.
Further, the dispersed phase solution in the step (1) comprises a regulator, and the addition amount is 0.05-0.2 g/mL.
Further, the regulator comprises fructo-oligosaccharides or glycerol.
Further, the mass fraction of the polysaccharide solution in the step (1) is 2-5%; the mass fraction of the hydrophobic polymer solution is 6-30%.
Further, in the step (2), the mass ratio of the dispersed phase solution to the continuous phase solution is 1:9-3:7.
Further, the homogenizing and emulsifying in the step (2) comprises one or more of rotor-stator homogenization, ultrasonic homogenization and high-pressure homogenization.
Further, the conditions of the electrostatic spinning in the step (3) are as follows: the spinning voltage is 8-20 kV, the spinning flow rate is 0.5-1.0 mL/h, the spinning distance is 10-15 cm, the spinning humidity is 30-60%, and the spinning temperature is 20-30 ℃.
The porous nano-carrier with adjustable morphology and aperture based on emulsion electrostatic spinning is prepared by the preparation method.
The porous nano-carrier with adjustable morphology and aperture based on emulsion electrostatic spinning is applied to the preparation of sensors or the analysis and detection fields.
The invention has the following beneficial effects:
(1) According to the invention, the polysaccharide solution is used as a disperse phase, the hydrophobic polymer solution is used as a continuous phase for nano-carrier preparation, and the nano-carriers with different morphologies or different apertures can be simply constructed by regulating and controlling the composition of the solution and adding low-viscosity solutes as regulators in the disperse phase, so that theoretical and method support is provided for controllable preparation of the porous nano-carrier, and a larger application space is promoted for application of the carrier in adsorption, immobilization, sensors and the like.
(2) The invention adopts a food-grade polymer one-step method to construct the porous nano material with adjustable aperture and morphology, and has larger application value and space in the food field than the traditional inorganic or organic nano porous material.
Drawings
FIG. 1 is a scanning electron microscope image of a nanocarrier of ethylcellulose prepared in comparative example 1;
FIG. 2 is a scanning electron microscope image of the porous nano-carrier with adjustable morphology and aperture based on emulsion electrostatic spinning prepared in comparative example 2;
FIG. 3 is a scanning electron microscope image of the porous nano-carrier with adjustable morphology and aperture based on emulsion electrostatic spinning prepared in example 1;
FIG. 4 is a scanning electron microscope image of the porous nano-carrier with adjustable morphology and aperture based on emulsion electrostatic spinning prepared in example 2;
FIG. 5 is a scanning electron microscope image of the porous nano-carrier with adjustable morphology and aperture based on emulsion electrostatic spinning prepared in example 3;
FIG. 6 is a scanning electron microscope image of the porous nano-carrier with adjustable morphology and aperture based on emulsion electrostatic spinning prepared in example 4;
FIG. 7 is a scanning electron microscope image of the porous nano-carrier with adjustable morphology and aperture based on emulsion electrostatic spinning prepared in example 5;
FIG. 8 is a scanning electron microscope image of the porous nano-carrier with adjustable morphology and aperture based on emulsion electrostatic spinning prepared in example 6;
FIG. 9 is a scanning electron microscope image of the porous nano-carrier with adjustable morphology and aperture based on emulsion electrostatic spinning prepared in example 7.
Detailed Description
The principles and features of the present invention are described below with reference to the drawings, the examples are illustrated for the purpose of illustrating the invention and are not to be construed as limiting the scope of the invention. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Example 1:
the preparation method of the porous nano-carrier with adjustable morphology and aperture based on emulsion electrostatic spinning comprises the following steps:
(1) 10mL of a 3% by mass aqueous pectin solution was prepared as the dispersed phase of the water-in-oil emulsion.
(2) An ethylcellulose solution (solvent is a mixed solution of chloroform and ethanol in a volume ratio of 3:1) with a mass fraction of 12% was prepared as a continuous phase of the water-in-oil emulsion.
(3) And (3) dropwise adding the disperse phase obtained in the step (1) into the continuous phase prepared in the step (2), wherein the mass ratio of the disperse phase to the continuous phase is 2:8, and carrying out combined ultrasonic treatment (3 min, amplitude 50%, 3s open 3 s) through a rotor-stator system (30000 rpm,5 min) to prepare the water-in-oil emulsion.
(4) Loading the water-in-oil emulsion obtained in the step (3) into an injector, and preparing the porous nano-carrier through an electrostatic spinning process (spinning voltage: 10kV, spinning flow rate: 1.0mL/h, spinning distance: 15cm, ambient humidity 45%, and ambient temperature: 25 ℃).
Example 2:
the preparation method of the porous nano-carrier with adjustable morphology and aperture based on emulsion electrostatic spinning comprises the following steps:
(1) 10mL of a 3% by mass aqueous pectin solution was prepared as the dispersed phase of the water-in-oil emulsion.
(2) An ethylcellulose solution (solvent is a mixed solution of chloroform and ethanol in a volume ratio of 3:1) with a mass fraction of 12% was prepared as a continuous phase of the water-in-oil emulsion.
(3) And (3) dropwise adding the disperse phase obtained in the step (1) into the continuous phase prepared in the step (2), wherein the mass ratio of the disperse phase to the continuous phase is 3:7, and carrying out combined ultrasonic treatment (3 min, amplitude 50%, 3s open 3 s) through a rotor-stator system (30000 rpm,5 min) to prepare the water-in-oil emulsion.
(4) Loading the water-in-oil emulsion obtained in the step (3) into an injector, and preparing the porous nano-carrier through an electrostatic spinning process (spinning voltage: 10kV, spinning flow rate: 1.0mL/h, spinning distance: 15cm, ambient humidity 45%, and ambient temperature: 25 ℃).
Example 3:
the preparation method of the porous nano-carrier with adjustable morphology and aperture based on emulsion electrostatic spinning comprises the following steps:
(1) 10mL of a 2% by mass aqueous pectin solution was prepared as the dispersed phase of the water-in-oil emulsion.
(2) An ethylcellulose solution (solvent is a mixed solution of chloroform and ethanol in a volume ratio of 3:1) with a mass fraction of 12% was prepared as a continuous phase of the water-in-oil emulsion.
(3) And (3) dropwise adding the disperse phase obtained in the step (1) into the continuous phase prepared in the step (2), wherein the mass ratio of the disperse phase to the continuous phase is 3:7, and carrying out combined ultrasonic treatment (3 min, amplitude 50%, 3s open 3 s) through a rotor-stator system (30000 rpm,5 min) to prepare the water-in-oil emulsion.
(4) Loading the water-in-oil emulsion obtained in the step (3) into an injector, and preparing the porous nano-carrier through an electrostatic spinning process (spinning voltage: 10kV, spinning flow rate: 1.0mL/h, spinning distance: 15cm, ambient humidity 45%, and ambient temperature: 25 ℃).
Example 4:
the preparation method of the porous nano-carrier with adjustable morphology and aperture based on emulsion electrostatic spinning comprises the following steps:
(1) 10mL of a 2% by mass aqueous pectin solution was prepared, and 0.5g of fructooligosaccharide powder (Santa Clara Biotechnology Co., ltd. In YunFu-Po) was added thereto and stirred well as a dispersed phase of a water-in-oil emulsion.
(2) An ethylcellulose solution (solvent is a mixed solution of chloroform and ethanol in a volume ratio of 3:1) with a mass fraction of 12% was prepared as a continuous phase of the water-in-oil emulsion.
(3) And (3) dropwise adding the disperse phase obtained in the step (1) into the continuous phase prepared in the step (2), wherein the mass ratio of the disperse phase to the continuous phase is 3:7, and carrying out combined ultrasonic treatment (3 min, amplitude 50%, 3s open 3 s) through a rotor-stator system (30000 rpm,5 min) to prepare the water-in-oil emulsion.
(4) Loading the water-in-oil emulsion obtained in the step (3) into an injector, and preparing the porous nano-carrier through an electrostatic spinning process (spinning voltage: 10kV, spinning flow rate: 1.0mL/h, spinning distance: 15cm, ambient humidity 45%, and ambient temperature: 25 ℃).
Example 5:
the preparation method of the porous nano-carrier with adjustable morphology and aperture based on emulsion electrostatic spinning comprises the following steps:
(1) 10mL of a 2% by mass aqueous pectin solution was prepared, and 1.0g of fructooligosaccharide powder (Santa Clara Biotechnology Co., ltd. In YunFu-Po) was added thereto and stirred well as a dispersed phase of a water-in-oil emulsion.
(2) An ethylcellulose solution (solvent is a mixed solution of chloroform and ethanol in a volume ratio of 3:1) with a mass fraction of 12% was prepared as a continuous phase of the water-in-oil emulsion.
(3) And (3) dropwise adding the disperse phase obtained in the step (1) into the continuous phase prepared in the step (2), wherein the mass ratio of the disperse phase to the continuous phase is 3:7, and carrying out combined ultrasonic treatment (3 min, amplitude 50%, 3s open 3 s) through a rotor-stator system (30000 rpm,5 min) to prepare the water-in-oil emulsion.
(4) Loading the water-in-oil emulsion obtained in the step (3) into an injector, and preparing the porous nano-carrier through an electrostatic spinning process (spinning voltage: 10kV, spinning flow rate: 1.0mL/h, spinning distance: 15cm, ambient humidity 45%, and ambient temperature: 25 ℃).
Example 6:
the preparation method of the porous nano-carrier with adjustable morphology and aperture based on emulsion electrostatic spinning comprises the following steps:
(1) 10mL of a 2% by mass aqueous pectin solution was prepared, and 1.5g of fructooligosaccharide powder (Santa Clara Biotechnology Co., ltd. In YunFu-Po) was added thereto and stirred well as a dispersed phase of a water-in-oil emulsion.
(2) An ethylcellulose solution (solvent is a mixed solution of chloroform and ethanol in a volume ratio of 3:1) with a mass fraction of 12% was prepared as a continuous phase of the water-in-oil emulsion.
(3) And (3) dropwise adding the disperse phase obtained in the step (1) into the continuous phase prepared in the step (2), wherein the mass ratio of the disperse phase to the continuous phase is 3:7, and carrying out combined ultrasonic treatment (3 min, amplitude 50%, 3s open 3 s) through a rotor-stator system (30000 rpm,5 min) to prepare the water-in-oil emulsion.
(4) Loading the water-in-oil emulsion obtained in the step (3) into an injector, and preparing the porous nano-carrier through an electrostatic spinning process (spinning voltage: 10kV, spinning flow rate: 1.0mL/h, spinning distance: 15cm, ambient humidity 45%, and ambient temperature: 25 ℃).
Example 7:
the preparation method of the porous nano-carrier with adjustable morphology and aperture based on emulsion electrostatic spinning comprises the following steps:
(1) 10mL of a 2% by mass pectin aqueous solution was prepared, and 2.0g of fructooligosaccharide powder (Santa Clara Biotechnology Co., ltd. In YunFu-Po) was added thereto and stirred well as a dispersed phase of a water-in-oil emulsion.
(2) An ethylcellulose solution (solvent is a mixed solution of chloroform and ethanol in a volume ratio of 3:1) with a mass fraction of 12% was prepared as a continuous phase of the water-in-oil emulsion.
(3) And (3) dropwise adding the disperse phase obtained in the step (1) into the continuous phase prepared in the step (2), wherein the mass ratio of the disperse phase to the continuous phase is 3:7, and carrying out combined ultrasonic treatment (3 min, amplitude 50%, 3s open 3 s) through a rotor-stator system (30000 rpm,5 min) to prepare the water-in-oil emulsion.
(4) Loading the water-in-oil emulsion obtained in the step (3) into an injector, and preparing the porous nano-carrier through an electrostatic spinning process (spinning voltage: 10kV, spinning flow rate: 1.0mL/h, spinning distance: 15cm, ambient humidity 45%, and ambient temperature: 25 ℃).
Comparative example 1:
the preparation method of the ethyl cellulose-based nano-carrier comprises the following steps:
(1) An ethyl cellulose solution with a mass fraction of 12% (the solvent is a mixed solution of chloroform and ethanol with a volume ratio of 3:1) was prepared.
(2) Loading the ethyl cellulose solution obtained in the step (1) into a syringe, and preparing the nano-carrier through an electrostatic spinning process (spinning voltage: 10kV, spinning flow rate: 1.0mL/h, spinning distance: 15cm, ambient humidity 45%, and ambient temperature: 25 ℃).
Comparative example 2:
the preparation method of the porous nano-carrier with adjustable morphology and aperture based on emulsion electrostatic spinning comprises the following steps:
(1) 10mL of a 3% by mass aqueous pectin solution was prepared as the dispersed phase of the water-in-oil emulsion.
(2) An ethyl cellulose solution with a mass fraction of 12% (the solvent is a mixed solution of chloroform and ethanol with a volume ratio of 3:1) was prepared.
(3) And (3) dropwise adding the disperse phase obtained in the step (1) into the continuous phase prepared in the step (2), wherein the mass ratio of the disperse phase to the continuous phase is 1:9, and carrying out combined ultrasonic treatment (3 min, amplitude 50%, 3s open 3 s) through a rotor-stator system (30000 rpm,5 min) to prepare the water-in-oil emulsion.
(4) Loading the water-in-oil emulsion obtained in the step (3) into an injector, and preparing the porous nano-carrier through an electrostatic spinning process (spinning voltage: 10kV, spinning flow rate: 1.0mL/h, spinning distance: 15cm, ambient humidity 45%, and ambient temperature: 25 ℃).
Test example:
the nanocarriers prepared in examples 1 to 7 and comparative examples 1 to 2 were photographed by a scanning electron microscope.
The morphology of the nano-carrier prepared in the comparative example 1 is shown in figure 1, the surface of the fiber is smooth and has no holes, and the diameter of the fiber is about 200-400 nm.
The morphology of the nano-carrier prepared in comparative example 2 is shown in fig. 2, the morphology of the nano-carrier prepared in comparative example 2 is shown in fig. 2 on the basis of comparative example 1, and the water-in-oil emulsion is prepared by using ethyl cellulose solution as a continuous phase and using pectin aqueous solution with the concentration of 3% as a disperse phase on the basis of comparative example 1. During the spinning process, the organic solvent in the continuous phase can be quickly evaporated to cause the temperature of the surface of the fiber to be suddenly reduced, and water vapor in the environment is condensed on the surface of the fiber when the water vapor is cooled. Since ethylcellulose is poorly soluble in water, thermally induced phase separation occurs on the fiber surface. In addition, during the electrospinning process, solvent water contained in the dispersed phase migrates from the inside of the fiber to the surface and volatilizes, and phase separation also occurs on the path of solvent water migration. However, the proportion of the dispersed phase in comparative example 2 is low, and although the prepared nanofiber has no holes, the prepared nanofiber has pits and has obvious pore-forming tendency.
The morphology of the nano-carrier prepared in the example 1 is shown in fig. 3, when the ratio of the disperse phase to the continuous phase in the water-in-oil emulsion is increased to 2:8, the diameter of the prepared nano-fiber is about 400nm, a large number of pore structures exist on the surface of the fiber, and the pores are mostly oblate.
The morphology of the nano-carrier prepared in the example 2 and the example 3 is shown in fig. 4 and 5, and when the proportion of the dispersed phase is increased (3:7) or the concentration of the dispersed phase is reduced (2%), round hole fibers which are uniformly distributed and regular can be obtained. In particular, when the concentration of the dispersed phase in the water-in-oil emulsion is reduced to 2% by keeping the ratio of the dispersed phase to the continuous phase of the emulsion to be 3:7, the prepared nanofiber has better uniformity, the fiber diameter is about 400nm, the pore forming on the surface of the fiber is more uniform, and the pore shape is circular.
The morphology of the nano-carrier prepared in example 4 is shown in fig. 6, and on the basis of example 2, after 0.5g of fructo-oligosaccharide is added in the disperse phase in this example, the surface of the prepared nano-fiber is obviously changed, and the pore diameter of the nano-carrier is far smaller than that of the fiber surface of examples 1-2.
The morphology of the nanocarrier prepared in example 5 is shown in fig. 7, and when the amount of fructooligosaccharides added to the dispersion phase is increased to 1.0g, the prepared nanocarrier is changed from fiber to sphere, and the surface of the nanocarrier is still provided with uniform pores step by step.
The morphology of the nanocarrier prepared in example 6 is shown in fig. 8, and when the amount of fructo-oligosaccharide added into the dispersion phase is continuously increased to 1.5g, the prepared nanocarrier is mainly spherical, the surface of the spherical carrier is still provided with uniform pattern textures step by step, and then each texture is provided with tiny pores step by step uniformly.
The morphology of the nano-carrier prepared in example 7 is shown in fig. 9, when the amount of fructo-oligosaccharide added into the dispersion phase is increased to 2.0g, the surface pattern texture and the nano-pore structure of the nano-carrier are not changed obviously, but the shape of the carrier is concave from a sphere shape, so that a bowl-shaped structure is formed.
In summary, the pectin solution is used as a disperse phase, the ethyl cellulose solution is used as a continuous phase for nano-carrier preparation, and the nano-carriers with different morphologies or different apertures can be simply constructed by regulating and controlling the composition of the solution and adding fructo-oligosaccharides into the disperse phase, so that a larger application space is promoted for the application of the carrier in the aspects of adsorption, immobilization, sensors and the like.
The foregoing description of the preferred embodiments of the invention is not intended to limit the invention to the precise form disclosed, and any such modifications, equivalents, and alternatives falling within the spirit and scope of the invention are intended to be included within the scope of the invention.
Claims (10)
1. The preparation method of the porous nano-carrier with adjustable morphology and aperture based on emulsion electrostatic spinning is characterized by comprising the following steps:
(1) Preparing a polysaccharide solution as a disperse phase solution and a hydrophobic polymer solution as a continuous phase solution;
(2) Mixing the disperse phase solution obtained in the step (1) with the continuous phase solution, homogenizing and emulsifying to obtain water-in-oil emulsion;
(3) And (3) preparing the water-in-oil emulsion obtained in the step (2) through an electrostatic spinning technology.
2. The method for preparing the porous nano-carrier with adjustable morphology and aperture based on emulsion electrostatic spinning according to claim 1, wherein the polysaccharide in the step (1) comprises at least one of pectin and sodium alginate; the hydrophobic polymer comprises at least one of ethylcellulose, cellulose acetate, eudragit S100.
3. The preparation method of the porous nano-carrier with adjustable morphology and aperture based on emulsion electrostatic spinning of claim 1, wherein the dispersed phase solution in the step (1) further comprises a regulator, and the addition amount is 0.05-0.2 g/mL.
4. The method for preparing the porous nano-carrier with adjustable morphology and aperture based on emulsion electrostatic spinning according to claim 3, wherein the regulator comprises fructo-oligosaccharide or glycerin.
5. The preparation method of the porous nano-carrier with adjustable morphology and aperture based on emulsion electrostatic spinning of claim 1, wherein the mass fraction of the polysaccharide solution in the step (1) is 2-5%; the mass fraction of the hydrophobic polymer solution is 6-30%.
6. The preparation method of the porous nano-carrier with adjustable morphology and aperture based on emulsion electrostatic spinning of claim 1, wherein the mass ratio of the disperse phase solution to the continuous phase solution in the step (2) is 1:9-3:7.
7. The method for preparing the porous nano-carrier with adjustable morphology and aperture based on emulsion electrostatic spinning according to claim 1, wherein the homogenizing and emulsifying in the step (2) comprises one or more of rotor-stator homogenizing, ultrasonic homogenizing and high-pressure homogenizing.
8. The method for preparing the porous nano-carrier with adjustable morphology and aperture based on emulsion electrostatic spinning according to claim 1, wherein the conditions of electrostatic spinning in the step (3) are as follows: the spinning voltage is 8-20 kV, the spinning flow rate is 0.5-1.0 mL/h, the spinning distance is 10-15 cm, the spinning humidity is 30-60%, and the spinning temperature is 20-30 ℃.
9. Porous nano-carrier with adjustable morphology and aperture based on emulsion electrostatic spinning, characterized in that the porous nano-carrier is prepared by the preparation method according to any one of claims 1-8.
10. The application of the porous nano-carrier with adjustable morphology and aperture based on emulsion electrostatic spinning as claimed in claim 9 in the preparation of sensors or in the field of analysis and detection.
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