CN112315660A - Biodegradable nanofiber medical bandage and preparation method thereof - Google Patents
Biodegradable nanofiber medical bandage and preparation method thereof Download PDFInfo
- Publication number
- CN112315660A CN112315660A CN202011535601.4A CN202011535601A CN112315660A CN 112315660 A CN112315660 A CN 112315660A CN 202011535601 A CN202011535601 A CN 202011535601A CN 112315660 A CN112315660 A CN 112315660A
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- bandage
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- 238000002360 preparation method Methods 0.000 title claims abstract description 9
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Classifications
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- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/16—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one other macromolecular compound obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds as constituent
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- A61F13/00063—Accessories for dressings comprising medicaments or additives, e.g. odor control, PH control, debriding, antimicrobic
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- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
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- D01F1/00—General methods for the manufacture of artificial filaments or the like
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- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
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- D06M13/144—Alcohols; Metal alcoholates
- D06M13/148—Polyalcohols, e.g. glycerol or glucose
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
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- D06M13/244—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
- D06M13/282—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing phosphorus
- D06M13/292—Mono-, di- or triesters of phosphoric or phosphorous acids; Salts thereof
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
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Abstract
The invention discloses a biodegradable nanofiber medical bandage and a preparation method thereof. The repairing layer comprises a supporting layer and a repairing layer; the supporting layer is obtained by finishing common gauze by a hydrophobic finishing agent; constructing a repairing layer on the upper surface of the supporting layer; the repairing layer is mainly made of nano fibers with a skin-core structure. When the bandage is used, the nanofiber adsorbs redundant blood tissue fluid to keep the wound environment clean and avoid bacterial breeding; after the bandage absorbs tissue fluid and blood secreted from a wound, the change of the pH value triggers the hydrolysis of the cucurbituril shell, and the repair fluid flows out of the cucurbituril hydrolysis gap to realize the functions of hemostasis, blood coagulation and sterilization; the bandage prepared by the invention has long storage time and excellent antibacterial performance, the main components are biodegradable materials, the bandage can be directly buried in soil, the biodegradation rate is high, the environment pollution is small, and the bandage has high practicability.
Description
Technical Field
The invention relates to the technical field of medical bandages, in particular to a biodegradable nanofiber medical bandage and a preparation method thereof.
Background
A bandage is a common medical article used for bandaging wounds and affected parts and is mainly made of gauze, cotton cloth or synthetic fibers. The current bandages on the market have strong hydrophilicity, and gauze fibers can absorb a large amount of blood and tissue fluid when the wounds are bound, so that the hemostasis time is long, and the hemostasis effect is poor; ordinary bandage still can be with the wound tissue direct contact on skin surface, blood that gushes out in the wound, composition such as interstitial fluid directly is absorbed by the bandage, blood, interstitial fluid liquid just can take place to solidify after a period of time, bond wound and bandage, patient when changing the bandage, tear the wound that has already stopped blood once more very easily, cause secondary damage, increase the difficulty of changing dressings, the fibre liquid on the bandage takes place to drop and leave over the foreign matter rejection on the wound very easily when changing the bandage simultaneously. The common bandage has single function, poor hemostatic effect, easy deterioration of active components of the medicine on the bandage, short preservation time of the bandage and insufficient antibacterial and antiviral effects.
The yield of medical textiles in China is over 70 ten thousand tons every year, and large-scale consumption is needed after large-scale production. Bandages are disposable medical supplies that are incinerated, buried or otherwise placed in the open air as medical waste after use. The incineration of medical waste can produce a large amount of harmful gas, produce the pollution to the atmosphere, and directly bury again because the degradation rate is low excessively, influence soil environment stability, bring the threat to the existence of animal and microorganism in the soil, and open-air stacking again can cause the waste of land resource.
Therefore, there is a need for a biodegradable nanofiber medical bandage with good hemostatic effect, environmental protection and no pollution and a preparation method thereof to solve the above problems.
Disclosure of Invention
The invention aims to provide a biodegradable nanofiber medical bandage and a preparation method thereof, and aims to solve the problems in the background technology.
A biodegradable nanofiber medical bandage comprises a supporting layer and a repairing layer; the supporting layer is obtained by finishing common gauze by a hydrophobic finishing agent; and constructing a repairing layer on the upper surface of the supporting layer, wherein the repairing layer is mainly nano-fiber with a skin-core structure.
The bandage prepared by the invention needs to be used for directly facing the repair layer side to a wound on the skin surface. The repairing layer mainly comprises nano fibers with a shell-core structure, and the nano fibers are prepared by a shell layer spinning solution and a core layer spinning solution through a coaxial electrostatic spinning technology. The coaxial nanofiber has an ultra-high specific surface area and abundant pores, and can provide more adhesion sites for the adhesion nucleus diffusion of wound cells.
Further, the nano-fiber comprises a shell layer spinning solution and a core layer spinning solution, wherein the shell layer spinning solution and the core layer spinning solution are in a mass ratio of (1-3): 1; the core layer spinning solution has certain hydrophilicity and can adsorb blood and tissue fluid, and the mass ratio of the shell layer spinning solution to the core layer spinning solution should be controlled in order to avoid excessive adsorption of the repairing layer on the blood and the tissue fluid.
Firstly, activating hydroxyl on the surface of porous starch by using sodium dodecyl sulfate, N-dimethylformamide, dibutyltin dilaurate, triethylene diamine and other components to enable the surface of the porous starch to carry a large number of hydroxyl active groups, and then modifying the porous starch with isocyanate groups by utilizing reaction of diphenylmethane diisocyanate and the activated porous starch to obtain modified porous starch; mixing the modified porous starch, chitosan and alginic acid, and crosslinking under the action of a crosslinking agent glutaraldehyde to obtain a core layer spinning solution; the chitosan and alginic acid in the cross-linking agent core layer spinning solution are both natural polysaccharides and have excellent compatibility, biodegradability and antibacterial property. The chitosan contains a large amount of active groups such as amino, hydroxyl and the like, the alginic acid contains active groups such as amino, carboxyl and the like, and the modified porous starch contains active hydroxyl and isocyanate groups; esterification reaction, hydrogen bond reaction and condensation reaction are carried out among active groups of chitosan, alginic acid and modified porous starch to form a stable cross-linked network structure in a nanofiber core layer, so that the prepared nanofiber has excellent mechanical property and remarkable antibacterial property; due to the existence of the modified porous starch, the nanofiber core layer has certain water absorption performance;
further, the shell spinning solution comprises the following raw material components: 30-50 parts of gelatin, 30-50 parts of zein, 10-14 parts of nano functional microspheres and 18-22 parts of long-chain molecules in parts by weight; the core layer spinning solution comprises the following raw material components: 8-10 parts of modified porous starch, 30-50 parts of chitosan, 30-50 parts of alginic acid and 6-12 parts of cross-linking agent by weight; the cross-linking agent is glutaraldehyde; the silane coupling agent is KH 550.
Further, the nano functional microsphere comprises the following raw material components: 20-40 parts of a repair liquid, 10-12 parts of a silane coupling agent, 8-12 parts of graphene oxide, 12-20 parts of zinc nitrate hexahydrate, 15-18 parts of cucurbituril and 10-20 parts of sodium citrate; the long-chain molecule is C8O（CH2CH2O）9H; the modified porous starch comprises the following raw material components: 30-50 parts of porous starch, 10-15 parts of sodium dodecyl sulfate, 8-10 parts of N, N-dimethylformamide, 10-15 parts of dibutyltin dilaurate, 10-15 parts of triethylene diamine, 15-20 parts of diphenylmethane diisocyanate and 12-16 parts of trichloromethane.
Further, the components of the raw materials of the repair liquid are as follows; 20-40 parts of caffeic acid, 20-40 parts of caffeic acid phenethyl ester and 10-15 parts of aminomethylbenzoic acid.
The cucurbituril used in the invention is one or more of seven-element cucurbituril, eight-element cucurbituril and ten-element cucurbituril; the cucurbituril is a ring host compound with a hydrophobic cavity structure and a hydrophilic port; the port is further surrounded by a carbonyl group; according to the invention, zinc nitrate hexahydrate, cucurbituril and modified graphene oxide are mixed, and the modified graphene oxide has a hydrophobic cavity structure and a hydrophilic port; zinc nitrate hexahydrate performs a reduction reaction under the action of sodium citrate, zinc ions in the zinc nitrate hexahydrate are dissociated, the zinc ions are firstly attracted by graphene oxide and deposited in the graphene oxide, the zinc ions coordinate with a pair of electrons of a carbonyl atom at a melon ring port to form a complex, the zinc ions play a role of 'bridging' to introduce melon rings to the graphene oxide, a reducing agent sodium citrate can enable dissociated Zn2+ to continuously obtain electrons and generate zinc oxide, the zinc oxide has certain photocatalysis effect and bacteriostasis capacity, and the bacteriostasis performance of the nanofibers can be further enhanced.
According to the invention, firstly, a silane coupling agent KH550 is used for modifying graphene oxide, the KH550 is used as an amino silane coupling agent, the primary amino group contained in the silane coupling agent can perform nucleophilic substitution reaction with the epoxy functional group on the graphene oxide, the KH550 molecular chain is grafted to the graphene oxide, and the graphene oxide modified by the silane coupling agent has better dispersibility and is not easy to agglomerate; the silane coupling agent used in the present invention can react at pH =10-12, while the nano-functional microspheres in the present invention are easily decomposed under acidic conditions, and KH550 is preferably used to maintain the stability of the nano-functional microspheres; according to the nano-functional microsphere prepared by the invention, graphene oxide is modified by KH550, the graphene oxide contains a large amount of primary amino groups, the primary amino groups can be connected with isocyanate groups on modified porous starch in the core layer spinning solution, and the primary amino groups can also form Schiff bases with aldehyde groups on glutaraldehyde in the core layer spinning solution, so that the interface bonding force between the core layer spinning solution and the shell layer spinning solution is improved, a stable cross-linked network structure is formed in nano-fibers, and the mechanical property of the nano-fibers is improved.
According to the invention, caffeic acid phenethyl ester and aminomethylbenzoic acid are mixed to form a repair liquid, wherein the repair liquid is a hemostatic drug with a benzene ring structure, and a hydrophobic inner cavity of guanidino can generate a saturation effect with the benzene ring, so that the repair liquid is loaded into a hydrophobic cavity of cucurbituril; the cucurbituril has a rigid structure, is high in selectivity on the repair liquid, is stable in property, can well protect the repair liquid, and can prevent the repair liquid from being oxidized, deteriorated, reduced in pesticide effect and the like under the action of air.
Caffeic acid and aminomethylbenzoic acid in the repair liquid have wide sterilization, antivirus, hemostatic and blood coagulation effects, and can also inhibit the phosphodiesterase of rattlesnake venom; the 0-dihydroxy (catechol) phenyl structure contained in caffeic acid phenethyl ester can remove free radicals generated by wounds and accelerate wound healing; through the synergistic effect of the three components, the prepared bandage not only can greatly reduce the blood coagulation time for hemostasis, but also can inhibit the generation of bacterial viruses and accelerate the healing of wounds.
The shell spinning solution also contains long-chain molecules C8O（CH2CH2O）9H, one end of the long-chain monomer is a hydrophilic hydroxyl group, and the other end of the long-chain monomer is a hydrophobic long chain; the hydrophobic finishing agent is particularly added with hydroxyl silicone oil and carboxyl silicone oil, the hydroxyl of the hydroxyl silicone oil and the carboxyl of the carboxyl silicone oil can react with the hydroxyl, amino and other groups in the shell spinning solution, so that the nanofiber is tightly connected with the supporting layer and is not easy to fall off, the hydrophobic long chain of the long chain molecule in the shell spinning solution is connected with the hydroxyl silicone oil on the supporting layer and the oily molecule on the carboxyl silicone oil, the interface binding force between the supporting layer and the nanofiber is further enhanced, and the mechanical property of the bandage is improved.
Further, the hydrophobic finishing agent comprises the following raw material components: 30-40 parts of propylene glycol, 3-5 parts of hydroxyl silicone oil, 3-5 parts of carboxyl silicone oil, 8-10 parts of organosiloxane, 4-6 parts of lecithin and 20-30 parts of ammonia water.
A preparation method of a biodegradable nanofiber medical bandage comprises the following steps:
s1, preparing nano functional microspheres:
A. preparing a repairing liquid: mixing caffeic acid and caffeic acid phenethyl ester, placing into absolute ethyl alcohol, stirring, adding aminomethylbenzoic acid, and stirring to obtain repairing solution;
B. preparing modified graphene oxide:
1) putting a silane coupling agent into ethanol, stirring and dissolving to obtain a solution B;
2) placing the graphene oxide in deionized water, performing ultrasonic dispersion, adding the solution B, continuously stirring, performing suction filtration and washing to obtain modified graphene oxide;
C. synthesizing the nano functional microspheres:
1) mixing zinc nitrate hexahydrate and cucurbituril, and stirring to obtain a solution C;
2) placing the modified graphene oxide in ethylene glycol, stirring and dispersing, adding the solution C for ultrasonic dispersion, adding sodium citrate for continuous ultrasonic reaction, and adjusting the pH value to obtain a solution D;
3) placing the solution D in a high-pressure reaction kettle, filtering, washing and drying in vacuum to obtain powder A;
4) placing the powder A in a repair liquid for ultrasonic dispersion, evaporating redundant repair liquid, and drying to obtain nano functional microspheres;
s2, preparing a core layer spinning solution:
1) placing porous starch in a sodium dodecyl sulfate solution, and stirring to obtain a material A;
2) stirring and mixing N, N-dimethylformamide, dibutyl tin dilaurate and triethylene diamine, adding the material A, dropwise adding diphenylmethane diisocyanate, stirring, dropwise adding chloroform, ultrasonically dispersing, filtering, washing and drying to obtain modified porous starch;
3) placing chitosan and alginic acid in an ethanol solution, stirring and dissolving, adding modified porous starch, stirring and reacting, dropwise adding a cross-linking agent, and stirring to obtain a core layer spinning solution;
s3, preparing a shell spinning solution: uniformly mixing gelatin and zein, adding the nano functional microspheres and long-chain molecules, and stirring to obtain a shell spinning solution;
s4, preparing a bandage:
1) stirring propylene glycol, hydroxyl silicone oil, carboxyl silicone oil, organic siloxane, lecithin and ammonia water to obtain a hydrophobic finishing agent;
2) placing common gauze in a hydrophobic finishing agent for dipping, and placing the common gauze on an electrostatic spinning receiving plate after freeze drying to be used as a supporting layer for receiving nano fibers;
3) and preparing the core layer spinning solution and the shell layer spinning solution into the nano-fiber with a shell-core structure by adopting a coaxial electrostatic spinning process, collecting the nano-fiber on the supporting layer to obtain a repairing layer, and drying and sterilizing the repairing layer to obtain the bandage.
The method specifically comprises the following steps:
s1, preparing nano functional microspheres:
A. preparing a repairing liquid: mixing caffeic acid and caffeic acid phenethyl ester, placing in anhydrous ethanol, stirring for 2-3min, adding aminomethylbenzoic acid, stirring at 100-150r/min for 1-2min to obtain repairing solution;
B. preparing modified graphene oxide:
1) putting a silane coupling agent into ethanol, stirring and dissolving to obtain a solution B;
2) placing graphene oxide in deionized water at 35-55 ℃, ultrasonically dispersing for 10-15min, adding the solution B, continuously stirring for reacting for 2-3h, and performing suction filtration and washing to obtain modified graphene oxide;
C. synthesizing the nano functional microspheres:
1) mixing zinc nitrate hexahydrate and cucurbituril, and stirring to react for 30-50min to obtain a solution C;
2) placing the modified graphene oxide in ethylene glycol, stirring and dispersing for 20-30min, adding the solution C, performing ultrasonic dispersion for 10-20min, adding sodium citrate, and continuing ultrasonic reaction for 1-2h to obtain a solution D;
3) putting the solution D into a high-pressure reaction kettle, reacting for 3-8h, filtering, washing and drying in vacuum to obtain powder A;
4) placing the powder A in a repair liquid under the inert gas atmosphere and at the temperature of 35-38 ℃, ultrasonically dispersing for 20-30min, evaporating redundant repair liquid, and drying to obtain nano functional microspheres;
s2, preparing a core layer spinning solution:
1) placing porous starch in sodium dodecyl sulfate solution, and stirring and reacting at 28-34 deg.C for 10-40min to obtain material A;
2) stirring and mixing N, N-dimethylformamide, dibutyltin dilaurate and triethylene diamine, adding the material A, dropwise adding diphenylmethane diisocyanate under stirring at the constant temperature of 60-70 ℃, stirring for reacting for 1-2h, dropwise adding chloroform, ultrasonically dispersing for 10-30min, and performing suction filtration, washing and drying to obtain modified porous starch;
3) dissolving chitosan and alginic acid in ethanol solution at 30-35 deg.C under stirring, adding modified porous starch, stirring at 100-300r/min for reaction for 10-30min, increasing rotation speed to 500-600r/min, adding crosslinking agent dropwise under stirring, and stirring for 5-10min to obtain core layer spinning solution;
s3, preparing a shell spinning solution: mixing gelatin and zein uniformly at 30-35 deg.C, adding nanometer functional microsphere and long chain molecule, stirring at 500-600r/min for reaction for 30-50min to obtain shell spinning solution;
s4, preparing a bandage:
1) stirring propylene glycol, hydroxyl silicone oil, carboxyl silicone oil, organic siloxane, lecithin and ammonia water at the rotating speed of 800-1000r/min for 40-60min to obtain a hydrophobic finishing agent;
2) placing common gauze in a hydrophobic finishing agent for soaking for 3-5h, and placing the common gauze on an electrostatic spinning receiving plate after freeze drying to be used as a supporting layer for receiving nano fibers;
3) under the condition of voltage of 13-23kV, the nano-fiber with a shell-core structure is prepared from the core layer spinning solution and the shell layer spinning solution by adopting a coaxial electrostatic spinning process, collected on the supporting layer to obtain a repairing layer, and dried and disinfected to obtain the bandage.
Further, the mass fraction of the sodium dodecyl sulfate in the step S2. 1) is 4-6%.
Further, the reaction temperature set in the high-pressure reaction kettle in the step S1 is 85-95 ℃, and the reaction pressure is 10-12 MPa; step 2) in step S1. C also needs to adjust the pH value to 10-12; the cucurbituril is more stable in this environment.
Further, the steps S1-S4 are carried out in a nitrogen atmosphere; the impurities in the air are prevented from entering to influence the smooth proceeding of the reaction.
Compared with the prior art, the invention has the following beneficial effects: the main components of the shell layer nanofiber shell layer are gelatin and zein with hydrophobic properties, so that the problem that blood and tissue fluid are adhered to a repairing layer to cause the wound to be adhered to a bandage and cause secondary injury to the wound when the bandage is replaced can be solved. When the bandage is not used, the cucurbituril firmly wraps the repair liquid, so that the medicine is not released slowly, the problem of medicine slow release of the bandage under the condition of no use is avoided, and the storage period of the bandage is prolonged; when the bandage is used, the nanofiber core layer firstly absorbs blood and tissue fluid, so that redundant blood tissue fluid is absorbed to keep the wound environment clean, bacteria breeding is avoided, meanwhile, the blood meets the nano-functional microspheres in the nanofiber shell layer in the process of passing through pores on the nanofibers, as the pH values of human blood and tissue fluid are 6.9-7.5, the pH value of the environment of the nano-functional microspheres is rapidly reduced, the melon ring shell is partially hydrolyzed, and repair fluid flows out from a hydrolyzed gap of the melon ring, so that the effects of hemostasis, blood coagulation and sterilization are realized; the bandage prepared by the invention can automatically identify wounds and release hemostatic drugs, prolongs the storage time of the bandage, and has good mechanical property and strong antibacterial and antiviral abilities.
The main components of the bandage are biodegradable materials, so that the bandage is safe and environment-friendly, can be directly buried in soil, has high biodegradation rate, small environmental pollution, energy conservation and environmental protection, and has high practicability.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A biodegradable nanofiber medical bandage comprises a supporting layer and a repairing layer; the supporting layer is obtained by finishing common gauze by a hydrophobic finishing agent; and constructing a repairing layer on the upper surface of the supporting layer, wherein the repairing layer is mainly nano-fiber with a skin-core structure.
The nano-fiber comprises a shell layer spinning solution and a core layer spinning solution, wherein the mass ratio of the shell layer spinning solution to the core layer spinning solution is 1: 1; the hydrophobic finishing agent comprises the following raw material components: the coating comprises, by weight, 30 parts of propylene glycol, 3 parts of hydroxyl silicone oil, 3 parts of carboxyl silicone oil, 8 parts of organic siloxane, 4 parts of lecithin and 20 parts of ammonia water.
The shell layer spinning solution comprises the following raw material components: 30 parts of gelatin, 30 parts of zein, 10 parts of nano functional microspheres and 18 parts of long-chain molecules in parts by weight; the core layer spinning solution comprises the following raw material components: 8 parts of modified porous starch, 30 parts of chitosan, 30 parts of alginic acid and 6 parts of cross-linking agent.
The nano functional microsphere comprises the following raw material components: to be provided withThe repairing liquid comprises, by weight, 20 parts of repairing liquid, 10 parts of silane coupling agent, 8 parts of graphene oxide, 12 parts of zinc nitrate hexahydrate, 15 parts of cucurbituril and 10 parts of sodium citrate; the long-chain molecule is C8O（CH2CH2O）9H; the modified porous starch comprises the following raw material components: the adhesive comprises, by weight, 30 parts of porous starch, 10 parts of sodium dodecyl sulfate, 8 parts of N, N-dimethylformamide, 10 parts of dibutyl tin dilaurate, 10 parts of triethylene diamine, 15 parts of diphenylmethane diisocyanate and 12 parts of trichloromethane.
The repairing liquid comprises the following raw material components: the weight portion of the caffeic acid is 20 portions, the caffeic acid phenethyl ester is 20 portions, and the aminomethylbenzoic acid is 10 portions.
S1, preparing nano functional microspheres:
A. preparing a repairing liquid: mixing caffeic acid and caffeic acid phenethyl ester, placing in anhydrous ethanol, stirring for 2min, adding aminomethylbenzoic acid, stirring at 100r/min for 1min to obtain repairing solution;
B. preparing modified graphene oxide:
1) putting a silane coupling agent into ethanol, stirring and dissolving to obtain a solution B;
2) placing graphene oxide in deionized water at 35 ℃, ultrasonically dispersing for 10min, adding the solution B, continuously stirring for reacting for 2h, and performing suction filtration and washing to obtain modified graphene oxide;
C. synthesizing the nano functional microspheres:
1) mixing zinc nitrate hexahydrate and cucurbituril, and stirring to react for 30min to obtain a solution C;
2) placing the modified graphene oxide in ethylene glycol, stirring and dispersing for 20min, adding the solution C, performing ultrasonic dispersion for 10min, adding sodium citrate, adjusting the pH value to 10, and continuing ultrasonic reaction for 1h to obtain a solution D;
3) placing the solution D in a high-pressure reaction kettle, setting the reaction temperature at 85 ℃ and the reaction pressure at 10MPa, reacting for 3 hours, filtering, washing and drying in vacuum to obtain powder A;
4) placing the powder A in a repair liquid at 35 ℃ for ultrasonic dispersion for 20min, evaporating redundant repair liquid, and drying to obtain nano functional microspheres;
s2, preparing a core layer spinning solution:
1) placing porous starch in a sodium dodecyl sulfate solution with the mass fraction of 4%, and stirring and reacting for 10min at the temperature of 28 ℃ to obtain a material A;
2) stirring and mixing N, N-dimethylformamide, dibutyltin dilaurate and triethylene diamine, adding the material A, dropwise adding diphenylmethane diisocyanate under stirring at the constant temperature of 60 ℃, stirring for reacting for 1h, dropwise adding chloroform, ultrasonically dispersing for 10min, and performing suction filtration, washing and drying to obtain modified porous starch;
3) placing chitosan and alginic acid in an ethanol solution at 30 ℃, stirring and dissolving, adding modified porous starch, stirring and reacting at the rotating speed of 100r/min for 10min, increasing the rotating speed to 500r/min, dropwise adding a cross-linking agent while stirring, and stirring for 5min to obtain a core layer spinning solution;
s3, preparing a shell spinning solution: uniformly mixing gelatin and zein at 30 ℃, adding nano functional microspheres and long chain molecules, and stirring at the rotating speed of 500r/min for reaction for 30min to obtain a shell spinning solution;
s4, preparing a bandage:
1) stirring propylene glycol, hydroxyl silicone oil, carboxyl silicone oil, organic siloxane, lecithin and ammonia water at the rotating speed of 800r/min for 40min to obtain a hydrophobic finishing agent;
2) placing common gauze in a hydrophobic finishing agent for soaking for 3 hours, and placing the common gauze on an electrostatic spinning receiving plate after freeze drying to be used as a supporting layer for receiving nano fibers;
3) under the condition of 13kV voltage, the core layer spinning solution and the shell layer spinning solution are prepared into the nano-fiber with the shell-core structure by adopting a coaxial electrostatic spinning process, and the nano-fiber is collected on the supporting layer to obtain a repairing layer, and the repairing layer is dried and sterilized to obtain the bandage.
Example 2
A biodegradable nanofiber medical bandage comprises a supporting layer and a repairing layer; the supporting layer is obtained by finishing common gauze by a hydrophobic finishing agent; and constructing a repairing layer on the upper surface of the supporting layer, wherein the repairing layer is mainly nano-fiber with a skin-core structure.
The nano-fiber comprises a shell layer spinning solution and a core layer spinning solution, wherein the mass ratio of the shell layer spinning solution to the core layer spinning solution is 2: 1; the hydrophobic finishing agent comprises the following raw material components: the coating comprises, by weight, 35 parts of propylene glycol, 4 parts of hydroxyl silicone oil, 4 parts of carboxyl silicone oil, 9 parts of organic siloxane, 5 parts of lecithin and 25 parts of ammonia water.
The shell layer spinning solution comprises the following raw material components: 40 parts of gelatin, 40 parts of zein, 12 parts of nano functional microspheres and 20 parts of long-chain molecules in parts by weight; the core layer spinning solution comprises the following raw material components: 9 parts of modified porous starch, 40 parts of chitosan, 40 parts of alginic acid and 9 parts of cross-linking agent.
The nano functional microsphere comprises the following raw material components: the repairing liquid comprises, by weight, 30 parts of repairing liquid, 11 parts of silane coupling agent, 10 parts of graphene oxide, 16 parts of zinc nitrate hexahydrate, 17 parts of cucurbituril and 15 parts of sodium citrate; the long-chain molecule is C8O（CH2CH2O）9H; the modified porous starch comprises the following raw material components: the coating comprises, by weight, 40 parts of porous starch, 12 parts of sodium dodecyl sulfate, 9 parts of N, N-dimethylformamide, 13 parts of dibutyl tin dilaurate, 13 parts of triethylene diamine, 17 parts of diphenylmethane diisocyanate and 14 parts of trichloromethane.
The repairing liquid comprises the following raw material components: 30 parts of caffeic acid, 30 parts of caffeic acid phenethyl ester and 13 parts of aminomethylbenzoic acid.
S1, preparing nano functional microspheres:
A. preparing a repairing liquid: mixing caffeic acid and caffeic acid phenethyl ester, placing in anhydrous ethanol, stirring for 2.5min, adding aminomethylbenzoic acid, stirring at 130r/min for 1.5min to obtain repairing solution;
B. preparing modified graphene oxide:
1) putting a silane coupling agent into ethanol, stirring and dissolving to obtain a solution B;
2) placing graphene oxide in deionized water at 45 ℃, ultrasonically dispersing for 13min, adding the solution B, continuously stirring for reacting for 2.5h, and performing suction filtration and washing to obtain modified graphene oxide;
C. synthesizing the nano functional microspheres:
1) mixing zinc nitrate hexahydrate and cucurbituril, and stirring to react for 40min to obtain a solution C;
2) placing the modified graphene oxide in ethylene glycol, stirring and dispersing for 25min, adding the solution C, performing ultrasonic dispersion for 15min, adding sodium citrate, adjusting the pH value to 11, and continuing ultrasonic reaction for 1.5h to obtain a solution D;
3) placing the solution D in a high-pressure reaction kettle, setting the reaction temperature at 90 ℃ and the reaction pressure at 11MPa, reacting for 5 hours, filtering, washing and drying in vacuum to obtain powder A;
4) placing the powder A in a repair liquid at 36 ℃ for ultrasonic dispersion for 25min, evaporating redundant repair liquid, and drying to obtain nano functional microspheres;
s2, preparing a core layer spinning solution:
1) placing porous starch in a lauryl sodium sulfate solution with the mass fraction of 5%, and stirring and reacting for 30min at the temperature of 30 ℃ to obtain a material A;
2) stirring and mixing N, N-dimethylformamide, dibutyltin dilaurate and triethylene diamine, adding the material A, dropwise adding diphenylmethane diisocyanate under stirring at the constant temperature of 65 ℃, stirring for reacting for 1.5h, dropwise adding chloroform, ultrasonically dispersing for 20min, and performing suction filtration, washing and drying to obtain modified porous starch;
3) dissolving chitosan and alginic acid in ethanol solution at 32 deg.C under stirring, adding modified porous starch, stirring at 200r/min for 20min, increasing rotation speed to 550r/min, adding crosslinking agent under stirring, and stirring for 7min to obtain core layer spinning solution;
s3, preparing a shell spinning solution: uniformly mixing gelatin and zein at 32 ℃, adding nano functional microspheres and long-chain molecules, and stirring at the rotating speed of 550r/min for 40min to obtain a shell spinning solution;
s4, preparing a bandage:
1) stirring propylene glycol, hydroxyl silicone oil, carboxyl silicone oil, organic siloxane, lecithin and ammonia water at the rotating speed of 900r/min for 50min to obtain a hydrophobic finishing agent;
2) placing common gauze in a hydrophobic finishing agent for soaking for 4 hours, and placing the common gauze on an electrostatic spinning receiving plate after freeze drying to be used as a supporting layer for receiving nano fibers;
3) under the condition of 18kV voltage, the core layer spinning solution and the shell layer spinning solution are prepared into the nano-fiber with the shell-core structure by adopting a coaxial electrostatic spinning process, and the nano-fiber is collected on the supporting layer to obtain a repairing layer, and the repairing layer is dried and sterilized to obtain the bandage.
Example 3
A biodegradable nanofiber medical bandage comprises a supporting layer and a repairing layer; the supporting layer is obtained by finishing common gauze by a hydrophobic finishing agent; and constructing a repairing layer on the upper surface of the supporting layer, wherein the repairing layer is mainly nano-fiber with a skin-core structure.
The nano-fiber comprises a shell layer spinning solution and a core layer spinning solution, wherein the mass ratio of the shell layer spinning solution to the core layer spinning solution is 3: 1; the hydrophobic finishing agent comprises the following raw material components: the coating comprises, by weight, 40 parts of propylene glycol, 5 parts of hydroxyl silicone oil, 5 parts of carboxyl silicone oil, 10 parts of organic siloxane, 6 parts of lecithin and 30 parts of ammonia water.
The shell layer spinning solution comprises the following raw material components: 50 parts of gelatin, 50 parts of zein, 14 parts of nano functional microspheres and 22 parts of long-chain molecules in parts by weight; the core layer spinning solution comprises the following raw material components: 10 parts of modified porous starch, 50 parts of chitosan, 50 parts of alginic acid and 12 parts of cross-linking agent.
The nano functional microsphere comprises the following raw material components: the repairing liquid comprises, by weight, 40 parts of repairing liquid, 12 parts of silane coupling agent, 12 parts of graphene oxide, 20 parts of zinc nitrate hexahydrate, 18 parts of cucurbituril and 20 parts of sodium citrate; the long-chain molecule is C8O（CH2CH2O）9H; the modified porous starch comprises the following raw material components: the adhesive comprises, by weight, 50 parts of porous starch, 15 parts of sodium dodecyl sulfate, 10 parts of N, N-dimethylformamide, 15 parts of dibutyl tin dilaurate, 15 parts of triethylene diamine, 20 parts of diphenylmethane diisocyanate and 16 parts of trichloromethane.
The repairing liquid comprises the following raw material components: 40 parts of caffeic acid, 40 parts of caffeic acid phenethyl ester and 15 parts of aminomethylbenzoic acid.
S1, preparing nano functional microspheres:
A. preparing a repairing liquid: mixing caffeic acid and caffeic acid phenethyl ester, placing in anhydrous ethanol, stirring for 3min, adding aminomethylbenzoic acid, stirring at 150r/min for 2min to obtain repairing solution;
B. preparing modified graphene oxide:
1) putting a silane coupling agent into ethanol, stirring and dissolving to obtain a solution B;
2) placing graphene oxide in deionized water at 55 ℃, ultrasonically dispersing for 15min, adding the solution B, continuously stirring for reacting for 3h, and performing suction filtration and washing to obtain modified graphene oxide;
C. synthesizing the nano functional microspheres:
1) mixing zinc nitrate hexahydrate and cucurbituril, and stirring to react for 50min to obtain a solution C;
2) placing the modified graphene oxide in ethylene glycol, stirring and dispersing for 30min, adding the solution C, performing ultrasonic dispersion for 20min, adding sodium citrate, adjusting the pH value to 12, and continuing ultrasonic reaction for 2h to obtain a solution D;
3) placing the solution D in a high-pressure reaction kettle, setting the reaction temperature at 95 ℃ and the reaction pressure at 12MPa, reacting for 8 hours, filtering, washing and drying in vacuum to obtain powder A;
4) placing the powder A in a repair liquid at 38 ℃ for ultrasonic dispersion for 30min, evaporating redundant repair liquid, and drying to obtain nano functional microspheres;
s2, preparing a core layer spinning solution:
1) placing porous starch in a lauryl sodium sulfate solution with the mass fraction of 6%, and stirring and reacting for 40min at the temperature of 34 ℃ to obtain a material A;
2) stirring and mixing N, N-dimethylformamide, dibutyltin dilaurate and triethylene diamine, adding the material A, dropwise adding diphenylmethane diisocyanate under stirring at the constant temperature of 70 ℃, stirring for reacting for 2 hours, dropwise adding chloroform, ultrasonically dispersing for 30min, and performing suction filtration, washing and drying to obtain modified porous starch;
3) dissolving chitosan and alginic acid in ethanol solution at 35 deg.C under stirring, adding modified porous starch, stirring at 300r/min for 30min, increasing rotation speed to 600r/min, adding crosslinking agent under stirring, and stirring for 10min to obtain core layer spinning solution;
s3, preparing a shell spinning solution: mixing gelatin and zein uniformly at 35 ℃, adding nano functional microspheres and long chain molecules, and stirring at the rotating speed of 600r/min for reaction for 50min to obtain a shell spinning solution;
s4, preparing a bandage:
1) stirring propylene glycol, hydroxyl silicone oil, carboxyl silicone oil, organic siloxane, lecithin and ammonia water at the rotating speed of 1000r/min for 60min to obtain a hydrophobic finishing agent;
2) placing common gauze in a hydrophobic finishing agent for soaking for 5 hours, and placing the common gauze on an electrostatic spinning receiving plate after freeze drying to be used as a supporting layer for receiving nano fibers;
3) under the condition of 23kV voltage, the core layer spinning solution and the shell layer spinning solution are prepared into the nano-fiber with the shell-core structure by adopting a coaxial electrostatic spinning process, and the nano-fiber is collected on the supporting layer to obtain a repairing layer, and the repairing layer is dried and sterilized to obtain the bandage.
Experiment: the medical bandages obtained in examples and comparative examples were cut into medical bandage samples having a size of 2cm × 3cm, respectively, and subjected to the following experiments:
and (3) testing the antibacterial rate: the bacteriostasis rate of the candida albicans is tested according to the GB/T20944.3-2008 standard.
In vitro coagulation test: and (3) establishing an acute bleeding emergency animal model by using the bandage placed for 1 day, and performing abdominal anesthesia on the experimental rabbits by using anesthetic. The blood vessels were fully exposed, cut with a scalpel, allowed to bleed freely for 10s, and then subjected to hemostatic intervention using the bandages prepared in the examples and comparative examples, and the clotting time was recorded, with the results shown in the table below.
And (3) aging test: after the bandages obtained in each example and comparative example were normally stored for 12 months, the in vitro coagulation test described above was continued and the coagulation time was recorded.
And (3) testing the degradation rate: the medical bandage samples of the examples and comparative examples according to the invention were weighed and embedded in the soil, and after 60 days a sample was taken and the mass loss recorded. The degradation rate formula is: d = (m)0-mt）/m0X 100%: wherein m is0Is the original mass of the medical bandage sample before degradation; m istThe remaining mass of the medical bandage sample after 60 days of degradation.
As can be seen from the data in the table, the bandage prepared in the examples 1 to 3 has shorter blood coagulation time and better hemostatic effect; meanwhile, after the bandage is stored for 12 months, the blood coagulation time has no obvious change, which shows that the repair components of the bandage in the examples 1-3 do not deteriorate and lose with time, and the quality guarantee period is longer; the bandage prepared in the embodiment 1-3 has the bacteriostatic rate of more than 95 percent and has excellent bacteriostatic effect; after 60 days of burying test, the biodegradation rate of the bandage samples of the examples 1-3 is over 85 percent, the biodegradation effect is better, the environmental pollution is small, and the practicability is very high.
Example 4
The difference from the embodiment 3 is that modified porous starch is not added, and due to the lack of the modified porous starch, when the bandage is used, because the nano-fiber has hydrophobicity, blood cannot be adsorbed by the nano-fiber but is adsorbed by the supporting layer, the pH value environment of the nano-functional microsphere cannot be changed, the cucurbituril cannot be hydrolyzed and releases the medicine, the blood coagulation time is longer, and the hemostatic effect is poorer.
Example 5
The difference from the embodiment 3 is that the nano-functional microspheres are not added, and due to the lack of the nano-functional microspheres, the prepared bandage cannot release the repair liquid, the hemostatic effect is poor, and the bacteriostatic rate is insufficient.
Example 6
The difference from the embodiment 3 is that the repairing liquid is coated in the silica hydrogel with the slow release function, and because the silica hydrogel is provided with pores in the year, the repairing liquid continuously flows out of the pores on the silica hydrogel in the bandage storage process, and the hemostatic effect is greatly reduced after the bandage is stored for 12 months.
Comparative example: the common medical composite fiber bandage has the advantages of insufficient antibacterial rate, long blood coagulation time, poor hemostatic effect and low biodegradation rate.
From the above data and experiments, we can conclude that: the invention discloses a biodegradable nanofiber medical bandage and a preparation method thereof. The repairing layer comprises a supporting layer and a repairing layer; the supporting layer is obtained by finishing common gauze by a hydrophobic finishing agent; and constructing a repairing layer on the upper surface of the supporting layer, wherein the repairing layer is mainly nano-fiber with a skin-core structure. When the bandage is used, the nanofiber adsorbs redundant blood tissue fluid to keep the wound environment clean and avoid bacterial breeding, and as the pH values of human blood and tissue fluid are 6.9-7.5, the pH value of the environment of the nano functional microsphere is rapidly reduced, partial hydrolysis of the cucurbituril shell occurs, and the repair liquid flows out from the hydrolyzed gap of cucurbituril, so that the effects of hemostasis, blood coagulation and sterilization are realized; the bandage prepared by the invention can automatically identify wounds and release hemostatic drugs, prolongs the storage time of the bandage and has strong antibacterial capability.
The main components of the bandage are biodegradable materials, so that the bandage is safe and environment-friendly, can be directly buried in soil, has high biodegradation rate, small environmental pollution, energy conservation and environmental protection, and has high practicability.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A biodegradable nanofiber medical bandage, characterized in that: the repairing layer comprises a supporting layer and a repairing layer; the supporting layer is obtained by finishing common gauze by a hydrophobic finishing agent; constructing a repairing layer on the upper surface of the supporting layer; the repairing layer is mainly made of nano fibers with a skin-core structure.
2. The biodegradable nanofiber medical bandage as claimed in claim 1, wherein: the nano-fiber comprises a shell layer spinning solution and a core layer spinning solution, wherein the mass ratio of the shell layer spinning solution to the core layer spinning solution is (1-3): 1; the hydrophobic finishing agent comprises the following raw material components: 30-40 parts of propylene glycol, 3-5 parts of hydroxyl silicone oil, 3-5 parts of carboxyl silicone oil, 8-10 parts of organosiloxane, 4-6 parts of lecithin and 20-30 parts of ammonia water.
3. The biodegradable nanofiber medical bandage as claimed in claim 2, wherein: the shell layer spinning solution comprises the following raw material components: 30-50 parts of gelatin, 30-50 parts of zein, 10-14 parts of nano functional microspheres and 18-22 parts of long-chain molecules in parts by weight; the core layer spinning solution comprises the following raw material components: 8-10 parts of modified porous starch, 30-50 parts of chitosan, 30-50 parts of alginic acid and 6-12 parts of cross-linking agent.
4. A biodegradable nanofiber medical bandage according to claim 3, characterized in that: the nano functional microsphere comprises the following raw material components: by weight, 20-40 parts of a repair liquid, 10-12 parts of a silane coupling agent, 8-12 parts of graphene oxide, 12-20 parts of zinc nitrate hexahydrate, 15-18 parts of cucurbituril and 10-20 parts of sodium citrate; the long-chain molecule is C8O（CH2CH2O）9H; the modified porous starch comprises the following raw material components: 30-50 parts of porous starch, 10-15 parts of sodium dodecyl sulfate, 8-10 parts of N, N-dimethylformamide, 10-15 parts of dibutyltin dilaurate, 10-15 parts of triethylene diamine, 15-20 parts of diphenylmethane diisocyanate and 12-16 parts of trichloromethane.
5. The biodegradable nanofiber medical bandage as claimed in claim 4, wherein: the repairing liquid comprises the following raw material components: 20-40 parts of caffeic acid, 20-40 parts of caffeic acid phenethyl ester and 10-15 parts of aminomethylbenzoic acid.
6. A preparation method of a biodegradable nanofiber medical bandage is characterized by comprising the following steps: the method comprises the following steps:
s1, preparing nano functional microspheres:
A. preparing a repairing liquid: mixing caffeic acid and caffeic acid phenethyl ester, placing into absolute ethyl alcohol, stirring, adding aminomethylbenzoic acid, and stirring to obtain repairing solution;
B. preparing modified graphene oxide:
1) putting a silane coupling agent into ethanol, stirring and dissolving to obtain a solution B;
2) placing the graphene oxide in deionized water, performing ultrasonic dispersion, adding the solution B, continuously stirring, performing suction filtration and washing to obtain modified graphene oxide;
C. synthesizing the nano functional microspheres:
1) mixing zinc nitrate hexahydrate and cucurbituril, and stirring to obtain a solution C;
2) placing the modified graphene oxide in ethylene glycol, stirring and dispersing, adding the solution C for ultrasonic dispersion, adding sodium citrate for continuous ultrasonic reaction, and adjusting the pH value to obtain a solution D;
3) placing the solution D in a high-pressure reaction kettle, filtering, washing and drying in vacuum to obtain powder A;
4) placing the powder A in a repair liquid for ultrasonic dispersion, evaporating redundant repair liquid, and drying to obtain nano functional microspheres;
s2, preparing a core layer spinning solution:
1) placing porous starch in a sodium dodecyl sulfate solution, and stirring to obtain a material A;
2) stirring and mixing N, N-dimethylformamide, dibutyl tin dilaurate and triethylene diamine, adding the material A, dropwise adding diphenylmethane diisocyanate, stirring, dropwise adding chloroform, ultrasonically dispersing, filtering, washing and drying to obtain modified porous starch;
3) placing chitosan and alginic acid in an ethanol solution, stirring and dissolving, adding modified porous starch, stirring and reacting, dropwise adding a cross-linking agent, and stirring to obtain a core layer spinning solution;
s3, preparing a shell spinning solution: uniformly mixing gelatin and zein, adding the nano functional microspheres and long-chain molecules, and stirring to obtain a shell spinning solution;
s4, preparing a bandage:
1) stirring propylene glycol, hydroxyl silicone oil, carboxyl silicone oil, organic siloxane, lecithin and ammonia water to obtain a hydrophobic finishing agent;
2) placing common gauze in a hydrophobic finishing agent for dipping, and placing the common gauze on an electrostatic spinning receiving plate after freeze drying to be used as a supporting layer for receiving nano fibers;
3) and preparing the core layer spinning solution and the shell layer spinning solution into the nano-fiber with a shell-core structure by adopting a coaxial electrostatic spinning process, collecting the nano-fiber on the supporting layer to obtain a repairing layer, and drying and sterilizing the repairing layer to obtain the bandage.
7. The method of claim 6, wherein the biodegradable nanofiber medical bandage is prepared by the following steps: the method specifically comprises the following steps:
s1, preparing nano functional microspheres:
A. preparing a repairing liquid: mixing caffeic acid and caffeic acid phenethyl ester, placing in anhydrous ethanol, stirring for 2-3min, adding aminomethylbenzoic acid, stirring at 100-150r/min for 1-2min to obtain repairing solution;
B. preparing modified graphene oxide:
1) putting a silane coupling agent into ethanol, stirring and dissolving to obtain a solution B;
2) placing graphene oxide in deionized water at 35-55 ℃, ultrasonically dispersing for 10-15min, adding the solution B, continuously stirring for reacting for 2-3h, and performing suction filtration and washing to obtain modified graphene oxide;
C. synthesizing the nano functional microspheres:
1) mixing zinc nitrate hexahydrate and cucurbituril, and stirring to react for 30-50min to obtain a solution C;
2) placing the modified graphene oxide in ethylene glycol, stirring and dispersing for 20-30min, adding the solution C, performing ultrasonic dispersion for 10-20min, adding sodium citrate, and continuing ultrasonic reaction for 1-2h to obtain a solution D;
3) putting the solution D into a high-pressure reaction kettle, reacting for 3-8h, filtering, washing and drying in vacuum to obtain powder A;
4) placing the powder A in a repair liquid under the inert gas atmosphere and at the temperature of 35-38 ℃, ultrasonically dispersing for 20-30min, evaporating redundant repair liquid, and drying to obtain nano functional microspheres;
s2, preparing a core layer spinning solution:
1) placing porous starch in sodium dodecyl sulfate solution, and stirring and reacting at 28-34 deg.C for 10-40min to obtain material A;
2) stirring and mixing N, N-dimethylformamide, dibutyltin dilaurate and triethylene diamine, adding the material A, dropwise adding diphenylmethane diisocyanate under stirring at the constant temperature of 60-70 ℃, stirring for reacting for 1-2h, dropwise adding chloroform, ultrasonically dispersing for 10-30min, and performing suction filtration, washing and drying to obtain modified porous starch;
3) dissolving chitosan and alginic acid in ethanol solution at 30-35 deg.C under stirring, adding modified porous starch, stirring at 100-300r/min for reaction for 10-30min, increasing rotation speed to 500-600r/min, adding crosslinking agent dropwise under stirring, and stirring for 5-10min to obtain core layer spinning solution;
s3, preparing a shell spinning solution: mixing gelatin and zein uniformly at 30-35 deg.C, adding nanometer functional microsphere and long chain molecule, stirring at 500-600r/min for reaction for 30-50min to obtain shell spinning solution;
s4, preparing a bandage:
1) stirring propylene glycol, hydroxyl silicone oil, carboxyl silicone oil, organic siloxane, lecithin and ammonia water at the rotating speed of 800-1000r/min for 40-60min to obtain a hydrophobic finishing agent;
2) placing common gauze in a hydrophobic finishing agent for soaking for 3-5h, and placing the common gauze on an electrostatic spinning receiving plate after freeze drying to be used as a supporting layer for receiving nano fibers;
3) under the condition of voltage of 13-23kV, the nano-fiber with a shell-core structure is prepared from the core layer spinning solution and the shell layer spinning solution by adopting a coaxial electrostatic spinning process, collected on the supporting layer to obtain a repairing layer, and dried and disinfected to obtain the bandage.
8. The method of claim 7, wherein the biodegradable nanofiber medical bandage is prepared by the following steps: and in the step S2, the mass fraction of the sodium dodecyl sulfate in the step 1) is 4-6%.
9. The method of claim 7, wherein the biodegradable nanofiber medical bandage is prepared by the following steps: the reaction temperature set in the high-pressure reaction kettle in the step S1 is 85-95 ℃, and the reaction pressure is 10-12 MPa; step 2) in step S1. C also needs to adjust the pH value to 10-12.
10. The method of claim 7, wherein the biodegradable nanofiber medical bandage is prepared by the following steps: steps S1-S4 need to be performed all the way under a nitrogen atmosphere.
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