CN112999404B - Stretchable nanofiber membrane and preparation method and application thereof - Google Patents
Stretchable nanofiber membrane and preparation method and application thereof Download PDFInfo
- Publication number
- CN112999404B CN112999404B CN202110483874.7A CN202110483874A CN112999404B CN 112999404 B CN112999404 B CN 112999404B CN 202110483874 A CN202110483874 A CN 202110483874A CN 112999404 B CN112999404 B CN 112999404B
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- Prior art keywords
- nanofiber membrane
- chitosan
- polyurethane
- solution
- carrier
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- 239000012528 membrane Substances 0.000 title claims abstract description 67
- 239000002121 nanofiber Substances 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 229920001661 Chitosan Polymers 0.000 claims abstract description 56
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000010410 layer Substances 0.000 claims abstract description 26
- 229920002635 polyurethane Polymers 0.000 claims abstract description 25
- 239000004814 polyurethane Substances 0.000 claims abstract description 25
- 239000012792 core layer Substances 0.000 claims abstract description 24
- 229940124350 antibacterial drug Drugs 0.000 claims abstract description 23
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 19
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 9
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- 239000000243 solution Substances 0.000 claims description 56
- 238000009987 spinning Methods 0.000 claims description 40
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 36
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 31
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 30
- 239000000463 material Substances 0.000 claims description 22
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- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical compound NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 16
- BDNKZNFMNDZQMI-UHFFFAOYSA-N 1,3-diisopropylcarbodiimide Chemical compound CC(C)N=C=NC(C)C BDNKZNFMNDZQMI-UHFFFAOYSA-N 0.000 claims description 14
- BGRWYRAHAFMIBJ-UHFFFAOYSA-N diisopropylcarbodiimide Natural products CC(C)NC(=O)NC(C)C BGRWYRAHAFMIBJ-UHFFFAOYSA-N 0.000 claims description 14
- 238000002791 soaking Methods 0.000 claims description 14
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 14
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 14
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- 239000004433 Thermoplastic polyurethane Substances 0.000 claims description 10
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 10
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- NTGIIKCGBNGQAR-UHFFFAOYSA-N Rheoemodin Natural products C1=C(O)C=C2C(=O)C3=CC(O)=CC(O)=C3C(=O)C2=C1O NTGIIKCGBNGQAR-UHFFFAOYSA-N 0.000 description 8
- RHMXXJGYXNZAPX-UHFFFAOYSA-N emodin Chemical compound C1=C(O)C=C2C(=O)C3=CC(C)=CC(O)=C3C(=O)C2=C1O RHMXXJGYXNZAPX-UHFFFAOYSA-N 0.000 description 8
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- 230000000052 comparative effect Effects 0.000 description 6
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000001354 calcination Methods 0.000 description 4
- 230000002349 favourable effect Effects 0.000 description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 4
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- KCVTVKMPZQSSNU-UHFFFAOYSA-N 2-pyridin-4-ylethanethioyl chloride Chemical compound ClC(=S)CC1=CC=NC=C1 KCVTVKMPZQSSNU-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 238000005576 amination reaction Methods 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 229960003022 amoxicillin Drugs 0.000 description 2
- LSQZJLSUYDQPKJ-NJBDSQKTSA-N amoxicillin Chemical compound C1([C@@H](N)C(=O)N[C@H]2[C@H]3SC([C@@H](N3C2=O)C(O)=O)(C)C)=CC=C(O)C=C1 LSQZJLSUYDQPKJ-NJBDSQKTSA-N 0.000 description 2
- 229960002793 amoxicillin sodium Drugs 0.000 description 2
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- 239000003814 drug Substances 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000004310 lactic acid Substances 0.000 description 2
- 235000014655 lactic acid Nutrition 0.000 description 2
- ILVPFTMKCHREDJ-UHFFFAOYSA-N methyl 5-amino-2-fluorobenzoate Chemical compound COC(=O)C1=CC(N)=CC=C1F ILVPFTMKCHREDJ-UHFFFAOYSA-N 0.000 description 2
- 229960001994 mezlocillin sodium Drugs 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- LSQZJLSUYDQPKJ-UHFFFAOYSA-N p-Hydroxyampicillin Natural products O=C1N2C(C(O)=O)C(C)(C)SC2C1NC(=O)C(N)C1=CC=C(O)C=C1 LSQZJLSUYDQPKJ-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- 208000035143 Bacterial infection Diseases 0.000 description 1
- 208000032544 Cicatrix Diseases 0.000 description 1
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- 230000010100 anticoagulation Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 208000022362 bacterial infectious disease Diseases 0.000 description 1
- 230000008952 bacterial invasion Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 210000001124 body fluid Anatomy 0.000 description 1
- 239000010839 body fluid Substances 0.000 description 1
- 150000001718 carbodiimides Chemical class 0.000 description 1
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Classifications
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- General Chemical & Material Sciences (AREA)
- Toxicology (AREA)
- Manufacturing & Machinery (AREA)
- Dispersion Chemistry (AREA)
- Artificial Filaments (AREA)
- Materials For Medical Uses (AREA)
- Multicomponent Fibers (AREA)
- Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
The invention relates to the technical field of preparation of nano medical fiber materials, and particularly discloses a stretchable nano fiber membrane and a preparation method and application thereof. The stretchable nanofiber membrane has a core-shell structure, and the core layer comprises an aminated chitosan carrier and an antibacterial drug doped in the aminated carrier; the shell layer comprises a polyurethane carrier, and poly N-isopropylacrylamide and N-TiO which are doped in the polyurethane carrier2Active carbon. The stretchable nanofiber membrane is prepared by a coaxial electrostatic spinning technology. The nanofiber membrane prepared by the invention has the advantages of excellent tensile property, strong adsorption property, long bacteriostatic time and self-cleaning, can obviously improve the healing effect of a wound surface, and has wide application prospect in the field of medical dressings.
Description
Technical Field
The invention relates to the technical field of preparation of nano medical fiber materials, in particular to a stretchable nano fiber membrane and a preparation method and application thereof.
Background
The skin has the functions of blocking foreign matters and pathogens from invading, preventing body fluid from losing and the like, is not only an important protective barrier for a human body, but also an important component of an immune system of the organism, and when the skin of the human body is damaged, medical dressing is needed to be used for protecting wounds. Medical dressings are a skin substitute for temporarily covering wounds, and have the main function of absorbing wound exudate and avoiding bacterial infection. Therefore, medical dressings need to have bacteriostatic, hemostatic and certain mechanical properties, and particularly need to have stretchable properties at the positions of fingers, knees, joints, elbows and the like.
The chitosan is a basic polysaccharide with natural anti-coagulation property, has excellent biological activity and good biodegradability, simultaneously has certain effects of hemostasis, antibiosis and antiphlogosis and the like, and is beneficial to promoting the regeneration of wound tissues and reducing the generation of scars. However, the currently commonly used chitosan nanofiber dressing or hydrogel dressing and the like have weak binding force with the antibacterial drug, cannot achieve the effect of slowly releasing the antibacterial drug, has poor tensile property, cannot be well applied to movable joint parts, has long contact time with the skin, and can cause poor wound healing effect due to the fact that blood, oil stain and the like of skin wounds are always adhered to the dressing. Therefore, there is a need to develop a medical nanofiber membrane which has good tensile property, drug slow release effect and self-cleaning function.
Disclosure of Invention
Aiming at the problems that the chitosan medical dressing commonly used at present in the prior art is poor in stretchability, does not have a drug slow-release effect and cannot be self-cleaned, the invention provides a stretchable nanofiber membrane and a preparation method and application thereof.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
a stretchable nanofiber membrane has a core-shell structure, wherein a core layer comprises an aminated chitosan carrier and an antibacterial drug doped in the aminated carrier; the shell layer comprises a polyurethane carrier, and poly N-isopropylacrylamide and N-TiO which are doped in the polyurethane carrier2Active carbon.
The polyurethane in the present invention is a thermoplastic polyurethane elastomer rubber (TPU).
Compared with the prior art, the stretchable nanofiber membrane provided by the invention adopts the aminated modified chitosan as the carrier of the antibacterial drug, the antibacterial drug is adsorbed and combined in a large area through the amino groups on the molecular chain of the modified chitosan, the bonding force between the antibacterial drug and the chitosan and the loading capacity of the antibacterial drug on the chitosan are improved, meanwhile, the loss of the antibacterial drug in the process of preparing the nanofiber membrane can be reduced, so that the loading effectiveness of the antibacterial drug is improved, the antibacterial drug is used as the core layer to be coated by adopting the elastic polyurethane as the shell layer, the nanofiber membrane can have excellent stretchability, meanwhile, the temperature-sensitive poly-N-isopropylacrylamide is compounded in the polyurethane carrier, the instantaneous volume shock of the nanofiber membrane contacting the skin can be caused to be reduced, the pore diameter of the nanofiber is increased, and the slow release of the antibacterial drug in the pore structure is realized, the antibacterial time and effectiveness of the nanofiber membrane are improved, and in addition, the N-TiO with excellent adsorption performance and photocatalytic self-cleaning performance is compounded in the polyurethane carrier2The active carbon can make blood and oil stain contacted with the nanofiber membrane automatically decompose under visible light, improve self-cleaning property and antibacterial long-acting property of wound surface, and is doped with N-TiO2The activated carbon can also increase the adsorption effect of the shell layer on the antibacterial drugs, is beneficial to the migration of the antibacterial drugs from the core layer to the shell layer, and further improves the antibacterial long-acting property of the nanofiber membrane.
Preferably, the aminated chitosan is obtained by modifying chitosan by tetraethylenepentamine and diisopropylcarbodiimide.
Preferably, the amino group content in the aminated chitosan is 30% -33%.
The chitosan is modified by selecting tetraethylenepentamine and diisopropylcarbodiimide, so that the amino content in the modified chitosan can be obviously improved, and the amino content can reach 30-33%, thereby being beneficial to improving the loading capacity of antibacterial drugs in chitosan carriers.
Preferably, the mass ratio of the aminated chitosan carrier to the polyurethane carrier is 1: 7-22.
Preferably, the doping amount of the antibacterial drug in the aminated chitosan carrier is 10-50 wt%.
Preferably, the doping amount of the poly-N-isopropylacrylamide in the polyurethane carrier is 13 to 27 wt%.
Preferably, the N-TiO2The doping amount of the active carbon in the polyurethane carrier is 4-11 wt%.
The preferable proportion of the substances can ensure that the nanofiber membrane has good stretchability, slow release and self-cleaning performance, so that the nanofiber membrane has better wound healing capability.
The antibacterial agent in the invention is not particularly limited, and can be common antibacterial agents in the field, such as emodin, amoxicillin sodium, amoxicillin hydrochloride, mezlocillin sodium and the like.
Preferably, the N-TiO2The preparation method of the activated carbon comprises the following steps:
adding wood powder into an alkaline solution for soaking for 2-4h, filtering, and drying to obtain a soaking material; then evenly mixing the dipping material, the biuret and the titanium dioxide, calcining for 1.5-2.5h at the temperature of 400-500 ℃ in an inert atmosphere, filtering, washing and drying to obtain the N-TiO2Active carbon.
The invention also provides a preparation method of the stretchable nanofiber membrane, which comprises the following steps:
step one, uniformly mixing chitosan and organic amine, heating and refluxing for reaction, filtering, washing and drying to obtain aminated chitosan; the organic amine is a mixture of tetraethylenepentamine and diisopropylcarbodiimide;
step two, adding the aminated chitosan and the antibacterial agent into a dilute acid solution, and uniformly mixing to obtain a core layer spinning solution;
step three, adding wood powder into an alkaline solution for soaking for 2-4h, filtering and drying to obtain a soaking material; then the impregnating material, biuret and titanium dioxide are mixed evenly, calcined for 1.5 to 2.5 hours at the temperature of 400-500 ℃ in inert atmosphere, washed and dried to obtain N-TiO2Activated carbon;
step four, polyurethane, poly N-isopropyl acrylamide and N-TiO are added2Adding active carbon into an organic mixed solution of dimethylformamide and ethanol, and uniformly mixing to obtain a skin layer spinning solution;
and fifthly, respectively injecting the core layer spinning solution and the skin layer spinning solution into a coaxial electrostatic spinning device for electrostatic spinning, and drying the obtained electrospun fiber to obtain the stretchable nanofiber membrane.
The invention respectively dissolves the skin layer material and the core layer material in proper solvents, and adopts a coaxial electrostatic spinning technology to prepare the nanofiber membrane with the core-shell structure, wherein, along with the volatilization of the solvents and the forming process of the fiber membrane in the spinning process, the nanofiber with the porous structure can be constructed, the porous structure is favorable for improving the stretchability of the fiber membrane and the adsorption performance of the skin layer, meanwhile, the porous structure is also favorable for improving the loading capacity of the antibacterial drug in the core layer, and the slow release of the antibacterial drug in the porous structure is realized, so that the healing promotion performance of the nanofiber membrane is improved.
The preparation method of the stretchable nanofiber membrane provided by the invention is simple to operate, can realize the preparation of the stretchable nanofiber membrane with excellent healing capacity constructed by a one-step method, and has higher practical value.
Preferably, in the step one, the mass-to-volume ratio of the chitosan to the organic amine is 0.08-0.12:1, wherein the unit of mass is gram, and the unit of volume is milliliter; the volume ratio of tetraethylenepentamine to diisopropylcarbodiimide in the organic amine is 3-5: 1.
The preferred proportion of each substance in the first step is beneficial to obtaining the modified chitosan with high amino content.
Preferably, in the step one, the reflux reaction time is 2-4 h.
Preferably, in the second step, the mass ratio of the aminated chitosan to the dilute acid solution is 0.02-0.05: 1.
Preferably, in the second step, the mass ratio of the antibacterial drug to the dilute acid solution is 0.005-0.01: 1.
Preferably, the concentration of the dilute acid solution is 0.1-0.5 mol/L.
The optimal dosage of the antibacterial agent and the amination modified chitosan is beneficial to improving the loading capacity of the antibacterial agent on the amination modified chitosan.
Optionally, the dilute acid solution is a hydrochloric acid solution, an acetic acid solution or a lactic acid solution.
Preferably, in the third step, the mass volume ratio of the wood powder to the alkali solution is 1-2: 5; wherein the unit of mass is gram and the unit of volume is milliliter; the concentration of the alkali solution is 0.8-1.2 mol/L.
Optionally, the alkali solution is a potassium hydroxide solution with the concentration of 0.8-1.2 mol/L.
Preferably, in the third step, the mass ratio of the impregnating material to the biuret is 5-10: 1.5-4.
Preferably, in the third step, the mass ratio of the biuret to the titanium dioxide is 2-4: 1.
Preferably, in the third step, the temperature is raised to 400-500 ℃ by adopting a temperature programming manner, and the temperature raising rate is 1.5-2.5 ℃/min.
The preferred proportion of each substance in the third step can be increased to increase the content of N-TiO2The capacity on the active carbon is improved, the self-cleaning performance of the nanofiber membrane is improved, the stretching performance of a shell layer is not influenced, meanwhile, the active carbon with large specific surface area and rich pore structure can be obtained by heat preservation reaction at the temperature of 400 plus materials and 500 ℃ for 1.5-2.5h, the adsorption performance of the nanofiber membrane is improved, wound exudate is absorbed quickly, meanwhile, the optimized reaction condition is favorable for carrying out nitrogen doping on titanium dioxide, and N-TiO with good visible light responsiveness is obtained2And the self-cleaning property of the nanofiber membrane is improved, so that the wound healing is promoted.
Preferably, in step four, the polyurethane, poly N-isopropylacrylamide and N-TiO2The mass ratio of the active carbon to the active carbon is 18-22:3-5: 1-2.
Preferably, in the fourth step, the mass ratio of the polyurethane to the organic mixed solution is 0.18-0.22: 1.
Preferably, in the fourth step, the volume ratio of the dimethylformamide to the ethanol is 1-2: 1.
The preferable addition amount of the poly-N-isopropylacrylamide can improve the temperature sensitivity of the nanofiber membrane, so that the volume of the nanofiber membrane is suddenly reduced when the nanofiber membrane is in contact with the skin, the pore diameter of the nanofiber is increased, and the release of antibacterial drugs is promoted; preferred N-TiO compounds2The addition of the activated carbon can endow the nanofiber membrane with better self-cleaning performance and adsorption performance on the premise of not influencing the tensile performance of a shell layer.
The inert gas in the present invention is an inert gas which is conventional in the art, such as nitrogen, argon, and the like.
Preferably, in the fifth step, the mass ratio of the aminated chitosan in the skin layer spinning solution to the polyurethane in the core layer spinning solution is 1: 7-22.
Preferably, in step five, the parameters of electrostatic spinning are as follows: the distance between the nozzle and the aluminum foil is 10-15cm, the spinning voltage is 20-30kV, the core layer spinning flow rate is 0.5-1mL/h, the skin layer spinning flow rate is 1-2mL/h, and the humidity is 25% -35%.
The optimized electrostatic spinning parameters are favorable for obtaining the nanofiber membrane forming a continuous core/shell structure, so that a foundation is provided for slow release of the antibacterial agent, volatilization of a solvent is facilitated, the prepared nanofiber has a porous structure, antibacterial agent release and gas exchange are facilitated, bacterial invasion is prevented, wound exudate is effectively absorbed, a warm and moist wound healing environment is maintained, and accordingly wound healing is accelerated.
The invention also provides application of the stretchable nanofiber membrane in medical dressings.
The nanofiber membrane provided by the invention has the advantages of excellent tensile property, strong adsorption property, long bacteriostatic time and self-cleaning, can obviously improve the healing effect of a wound surface, can be suitable for wounds of different parts, especially movable joint parts, and has wide application prospect in the field of medical dressings.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
In order to better illustrate the invention, the following examples are given by way of further illustration.
Example 1
The embodiment of the invention provides a preparation method of a stretchable nanofiber membrane, which comprises the following steps:
step one, weighing 10g of chitosan, dissolving the chitosan into 100mL of a mixed solution of tetraethylenepentamine and diisopropylcarbodiimide, wherein the volume ratio of the tetraethylenepentamine to the diisopropylcarbodiimide is 5:1, heating, refluxing and reacting for 2h, cooling to room temperature, filtering, washing with absolute ethyl alcohol and water respectively, and drying to obtain aminated chitosan;
step two, adding 5mL of 0.3mol/L acetic acid solution into the aminated chitosan obtained in the step one, uniformly mixing, adding emodin, and performing ultrasonic treatment in a water bath at 50 ℃ for 2 hours to obtain a core layer spinning solution; wherein, the adding amount of the aminated chitosan is 2 wt% of the mass of the acetic acid solution, and the adding amount of the emodin is 1 wt% of the mass of the acetic acid solution;
step three, soaking 5g of wood powder in 25mL of 1.0mol/L KOH solution for 3h, filtering and drying to obtain a soaking material; uniformly mixing the impregnating material with biuret and titanium dioxide, heating to 450 ℃ at the speed of 2 ℃/min in the nitrogen atmosphere, calcining for 2h, washing to neutrality, and drying in vacuum at 120 ℃ to obtain N-TiO2Activated carbon; wherein the mass ratio of the impregnating material to biuret is 5: 4, the mass ratio of the biuret to the titanium dioxide is 2: 1;
step four, mixing the TPU, the poly N-isopropyl acrylamide and the N-TiO2Adding activated carbon into 10mL of organic mixed solution of dimethylformamide and ethanol, and mixing uniformly to obtain cortex textileSilk liquid; wherein the addition amount of the TPU is 20 wt% of the mass of the organic mixed solution, the addition amount of the poly N-isopropylacrylamide is 4 wt% of the mass of the organic mixed solution, and the N-TiO is2The adding amount of the active carbon is 1 wt% of the mass of the organic mixed solution; the volume ratio of the dimethylformamide to the ethanol in the organic mixed solution is 1: 1;
and step five, respectively filling the skin layer spinning solution and the core layer spinning solution into 10mL and 5mL injectors, connecting the injectors with a coaxial nozzle, simultaneously enabling the distance between the nozzle and the aluminum foil to be 12cm, the spinning voltage to be 20kV, the core layer spinning flow rate to be 1mL/h, the skin layer spinning flow rate to be 2mL/h and the humidity to be 30% for electrospinning, and carrying out vacuum drying on the prepared electrospun fiber membrane for 24h to obtain the stretchable nanofiber membrane.
And (3) determining the amino content of the aminated chitosan prepared in the second step by using an Element Analyzer (EA), wherein the amino content is determined to be 33%.
And (3) performance testing:
and calculating the bacteriostatic rate under the stretchable condition according to a method of the bacteriostatic rate in the standard GB/T20944.3-2008 'evaluation of antibacterial performance of textiles'.
The mechanical property of the nanofiber composite membrane is tested by using an electronic universal testing machine, the size of a sample is a rectangular sample strip of 5mm multiplied by 35mm, the gauge length is 20mm, and the testing speed is 4 mm/min.
The nanofiber membrane prepared in this example had a tensile strength of 35.4MPa and an elongation at break of 55.4%. The antibacterial rate under the condition that the stretching rate is 20 percent is 99.1 percent, and the antibacterial rates under the condition that the stretching rates after the use time is 2 hours, 4 hours and 6 hours are 20 percent are respectively 98.7 percent, 97.6 percent and 96.9 percent.
Example 2
The embodiment of the invention provides a preparation method of a stretchable nanofiber membrane, which comprises the following steps:
step one, weighing 10g of chitosan, dissolving the chitosan into 100mL of a mixed solution of tetraethylenepentamine and diisopropylcarbodiimide, wherein the volume ratio of the tetraethylenepentamine to the diisopropylcarbodiimide is 3:1, heating, refluxing, reacting for 4 hours, cooling to room temperature, filtering, washing with absolute ethyl alcohol and water respectively, and drying to obtain aminated chitosan;
step two, adding 5mL of 0.1mol/L acetic acid solution into the aminated chitosan obtained in the step one, uniformly mixing, adding emodin, and performing ultrasonic treatment in a water bath at 50 ℃ for 2 hours to obtain a core layer spinning solution; wherein, the adding amount of the aminated chitosan is 3 wt% of the mass of the acetic acid solution, and the adding amount of the emodin is 0.8 wt% of the mass of the acetic acid solution;
step three, soaking 10g of wood powder in 25mL of 1.0mol/L KOH solution for 2h, filtering and drying to obtain a soaking material; uniformly mixing the impregnating material with biuret and titanium dioxide, heating to 500 ℃ at the speed of 2.5 ℃/min in the nitrogen atmosphere, calcining for 1.5h, washing to neutrality, and vacuum drying at 120 ℃ to obtain N-TiO2Activated carbon; wherein the mass ratio of the impregnating material to the biuret is 10:1.5, and the mass ratio of the biuret to the titanium dioxide is 3: 1;
step four, mixing the TPU, the poly N-isopropyl acrylamide and the N-TiO2Adding activated carbon into 10mL of an organic mixed solution of dimethylformamide and ethanol, and uniformly mixing to obtain a skin layer spinning solution; wherein the addition amount of the TPU is 22 wt% of the organic mixed solution, the addition amount of the poly N-isopropylacrylamide is 3 wt% of the organic mixed solution, and the N-TiO is2The adding amount of the active carbon is 1.5 wt% of the mass of the organic mixed solution; the volume ratio of the dimethylformamide to the ethanol in the organic mixed solution is 1.5: 1;
and step five, respectively filling the skin layer spinning solution and the core layer spinning solution into 10mL and 5mL injectors, connecting the injectors with a coaxial nozzle, simultaneously enabling the distance between the nozzle and the aluminum foil to be 10cm, the spinning voltage to be 30kV, the core layer spinning flow rate to be 0.5mL/h, the skin layer spinning flow rate to be 1mL/h and the humidity to be 25%, carrying out electrospinning, and carrying out vacuum drying on the prepared electrospun fiber membrane for 24h to obtain the stretchable nanofiber membrane.
And (3) determining the amino content of the aminated chitosan prepared in the step two by using an Element Analyzer (EA), wherein the determined amino content is 32%.
The nanofiber membrane prepared in the example is subjected to antibacterial and mechanical property tests according to the test method of example 1, and the nanofiber membrane prepared in the example has the tensile strength of 38.2MPa and the elongation at break of 61.3%. The antibacterial rate under the condition of 20% of the elongation rate is 99.5%, and the antibacterial rates under the condition of 20% of the elongation rate after 2, 4 and 6 hours of use are respectively 98.9%, 98.3% and 97.9%.
Example 3
The embodiment of the invention provides a preparation method of a stretchable nanofiber membrane, which comprises the following steps:
weighing 10g of chitosan, dissolving the chitosan in 100mL of a mixed solution of tetraethylenepentamine and diisopropylcarbodiimide, wherein the volume ratio of the tetraethylenepentamine to the diisopropylcarbodiimide is 4:1, heating, refluxing, reacting for 3 hours, cooling to room temperature, filtering, washing with absolute ethyl alcohol and water respectively, and drying to obtain aminated chitosan;
step two, adding 5mL of 0.5mol/L acetic acid solution into the aminated chitosan obtained in the step one, uniformly mixing, adding emodin, and performing ultrasonic treatment in a water bath at 50 ℃ for 2 hours to obtain a core layer spinning solution; wherein, the adding amount of the aminated chitosan is 5 wt% of the mass of the acetic acid solution, and the adding amount of the emodin is 0.5 wt% of the mass of the acetic acid solution;
step three, soaking 8g of wood powder in 25mL of 1.0mol/L KOH solution for 4h, filtering, and drying to obtain a soaking material; uniformly mixing the impregnating material with biuret and titanium dioxide, heating to 400 ℃ at the speed of 1.5 ℃/min in the nitrogen atmosphere, calcining for 2.5h, washing to neutrality, and vacuum drying at 120 ℃ to obtain N-TiO2Activated carbon; wherein the mass ratio of the impregnating material to biuret is 8: 4, the mass ratio of the biuret to the titanium dioxide is 4: 1;
step four, mixing the TPU, the poly N-isopropyl acrylamide and the N-TiO2Adding activated carbon into 10mL of an organic mixed solution of dimethylformamide and ethanol, and uniformly mixing to obtain a skin layer spinning solution; wherein the addition amount of the TPU is 18 wt% of the mass of the organic mixed solution, the addition amount of the poly N-isopropylacrylamide is 5 wt% of the mass of the organic mixed solution, and the N-TiO is2The adding amount of the active carbon is 2 wt% of the mass of the organic mixed solution; the volume ratio of the dimethylformamide to the ethanol in the organic mixed solution is 2: 1;
and step five, respectively filling the skin layer spinning solution and the core layer spinning solution into 10mL and 5mL injectors, connecting the injectors with a coaxial nozzle, simultaneously enabling the distance between the nozzle and the aluminum foil to be 15cm, the spinning voltage to be 25kV, the core layer spinning flow rate to be 0.8mL/h, the skin layer spinning flow rate to be 1.6mL/h and the humidity to be 35%, carrying out electrospinning, and carrying out vacuum drying on the prepared electrospun fiber membrane for 24h to obtain the stretchable nanofiber membrane.
And (3) determining the amino content of the aminated chitosan prepared in the step two by using an Element Analyzer (EA), wherein the amino content is determined to be 31%.
The nanofiber membrane prepared in the embodiment is subjected to antibacterial and mechanical property tests according to the test method of the embodiment 1, and the nanofiber membrane prepared in the embodiment has the tensile strength of 32.2MPa and the elongation at break of 50.1%. The antibacterial rate under the condition that the stretching rate is 20 percent is 99.2 percent, and the antibacterial rates under the condition that the stretching rates after the use time is 2 hours, 4 hours and 6 hours are 20 percent are respectively 98.8 percent, 97.9 percent and 96.8 percent.
The acetic acid solution in the second step of examples 1 to 3 may be replaced by a hydrochloric acid solution or a lactic acid solution, and the emodin may be replaced by other antibacterial agents, such as amoxicillin sodium, amoxicillin hydrochloride, mezlocillin sodium, and the like, which all achieve the technical effects substantially equivalent to those of examples 1 to 3.
Comparative example 1
This comparative example provides a method of preparing a stretchable nanofiber membrane exactly the same as example 1 except that no N-TiO was added to the shell spinning solution2Active carbon.
The prepared nanofiber membrane is subjected to antibacterial performance and mechanical performance tests according to the test method of example 1, and the nanofiber membrane prepared in the comparative example has the tensile strength of 32MPa and the elongation at break of 52.8%, the bacteriostasis rate under the condition that the tensile rate is 20% is 97.1%, and the bacteriostasis rates under the conditions that the tensile rates after the use time is 2 hours, 4 hours and 6 hours are 20% are 87.1%, 75.1% and 71.1% respectively.
Comparative example 2
This comparative example provides a stretchable nanofiber membrane prepared exactly the same as example 1 except that tetraethylenepentamine and diisopropylcarbodiimide were replaced with equal amounts of triethylenetetramine and carbodiimide in step one.
The prepared nanofiber membrane is tested for antibacterial performance and mechanical performance according to the testing method of example 1, and the nanofiber membrane prepared in the comparative example has the tensile strength of 32MPa and the elongation at break of 52.5%. The bacteriostatic ratio under the condition of 20 percent of the elongation rate is 93.3 percent, and the bacteriostatic ratios under the condition of 20 percent of the elongation rate after 2, 4 and 6 hours of use are 84.2 percent, 72.8 percent and 69.3 percent respectively.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents or improvements made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (8)
1. A stretchable nanofiber membrane, which is characterized by having a core-shell structure, wherein the core layer comprises an aminated chitosan carrier and an antibacterial drug doped in the aminated carrier; the shell layer comprises a polyurethane carrier, and poly N-isopropylacrylamide and N-TiO which are doped in the polyurethane carrier2Activated carbon;
wherein the polyurethane is a thermoplastic polyurethane elastomer rubber (TPU); the aminated chitosan is obtained by modifying chitosan by tetraethylenepentamine and diisopropylcarbodiimide, and the amino content in the aminated chitosan is 30-33%;
the N-TiO compound2The preparation method of the activated carbon comprises the following steps:
adding wood powder into an alkaline solution for soaking for 2-4h, filtering, and drying to obtain a soaking material; the impregnating material, the biuret and the titanium dioxide are evenly mixed, calcined for 1.5 to 2.5 hours at the temperature of 400-500 ℃ in an inert atmosphere, washed and dried to obtain the N-TiO2Active carbon.
2. The stretchable nanofiber membrane according to claim 1, wherein the mass ratio of the aminated chitosan carrier to the polyurethane carrier is 1: 7-22; and/or
The doping amount of the antibacterial drug in the aminated chitosan carrier is 10-50 wt%; and/or
The doping amount of the poly N-isopropylacrylamide in the polyurethane carrier is 13-27 wt%; and/or
The N-TiO compound2The doping amount of the active carbon in the polyurethane carrier is 4-11 wt%.
3. A method of making a stretchable nanofiber membrane as claimed in any one of claims 1-2 comprising the steps of:
step one, uniformly mixing chitosan and organic amine, heating and refluxing for reaction, filtering, washing and drying to obtain aminated chitosan; the organic amine is a mixture of tetraethylenepentamine and diisopropylcarbodiimide;
step two, adding the aminated chitosan and the antibacterial agent into a dilute acid solution, and uniformly mixing to obtain a core layer spinning solution;
step three, adding wood powder into an alkaline solution for soaking for 2-4h, filtering and drying to obtain a soaking material; the impregnating material, the biuret and the titanium dioxide are evenly mixed, calcined for 1.5 to 2.5 hours at the temperature of 400-500 ℃ in an inert atmosphere, washed and dried to obtain the N-TiO2Activated carbon;
step four, polyurethane, poly N-isopropyl acrylamide and N-TiO are added2Adding active carbon into an organic mixed solution of dimethylformamide and ethanol, and uniformly mixing to obtain a skin layer spinning solution;
and fifthly, respectively injecting the core layer spinning solution and the skin layer spinning solution into a coaxial electrostatic spinning device for electrostatic spinning, and drying the obtained electrospun fiber to obtain the stretchable nanofiber membrane.
4. The method for preparing a stretchable nanofiber membrane according to claim 3, wherein in the first step, the mass-to-volume ratio of chitosan to organic amine is 0.08-0.12:1, wherein the unit of mass is gram and the unit of volume is milliliter; the volume ratio of tetraethylenepentamine to diisopropylcarbodiimide in the organic amine is 3-5: 1; and/or
In the second step, the mass ratio of the aminated chitosan to the dilute acid solution is 0.02-0.05: 1; and/or
In the second step, the mass ratio of the antibacterial drug to the dilute acid solution is 0.005-0.01: 1.
5. The method for preparing stretchable nanofiber membrane as claimed in claim 3, wherein in the third step, the mass volume ratio of the wood powder to the alkali solution is 1-2: 5; wherein the unit of mass is gram and the unit of volume is milliliter; the concentration of the alkali solution is 0.8-1.2 mol/L;
in the third step, the mass ratio of the impregnating material to the biuret is 5-10: 1.5-4; and/or
In the third step, the mass ratio of the biuret to the titanium dioxide is 2-4: 1; and/or
In the third step, the temperature is raised to 400-500 ℃ by adopting a programmed temperature raising mode, and the temperature raising rate is 1.5-2.5 ℃/min.
6. The method of preparing a stretchable nanofiber membrane according to claim 3, wherein in step four, the polyurethane, poly N-isopropylacrylamide and N-TiO are2The mass ratio of the active carbon to the active carbon is 18-22:3-5: 1-2; and/or
In the fourth step, the mass ratio of the polyurethane to the organic mixed solution is 0.18-0.22: 1; and/or
In the fourth step, the volume ratio of the dimethyl formamide to the ethanol is 1-2: 1.
7. The method for preparing the stretchable nanofiber membrane as claimed in claim 3, wherein in the fifth step, the mass ratio of the aminated chitosan in the skin layer spinning solution to the polyurethane in the core layer spinning solution is 1: 7-22; and/or
In the fifth step, the electrostatic spinning parameters are as follows: the distance between the nozzle and the aluminum foil is 10-15cm, the spinning voltage is 20-30kV, the core layer spinning flow rate is 0.5-1mL/h, the skin layer spinning flow rate is 1-2mL/h, and the humidity is 25% -35%.
8. Use of a stretchable nanofibrous membrane according to any of claims 1-2 for the preparation of a medical dressing.
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| JP2022541309A JP7288148B2 (en) | 2021-04-30 | 2022-02-10 | Stretchable nanofiber film and its manufacturing method and application |
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| CN112999404B (en) * | 2021-04-30 | 2022-01-11 | 河北宁纺集团有限责任公司 | Stretchable nanofiber membrane and preparation method and application thereof |
| CN115212339A (en) * | 2022-07-20 | 2022-10-21 | 浙江红雨医药用品有限公司 | Active carbon polyurethane foam dressing and preparation method thereof |
| CN116905117B (en) * | 2022-11-25 | 2024-04-26 | 吴江福华织造有限公司 | Functional fiber, application thereof and fabric |
| CN116005363A (en) * | 2023-01-17 | 2023-04-25 | 河北科技大学 | Stretchable boron-nitrogen doped manganese dioxide nanofiber membrane and preparation method and application thereof |
| CN116905119A (en) * | 2023-06-29 | 2023-10-20 | 山东大学 | Preparation method of TNF/TPU composite fiber with high tensile strength |
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| JP7288148B2 (en) | 2023-06-06 |
| CN112999404A (en) | 2021-06-22 |
| ZA202207102B (en) | 2022-07-27 |
| WO2022161505A1 (en) | 2022-08-04 |
| JP2023507665A (en) | 2023-02-24 |
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