CN111171361A - Bacterial cellulose composite membrane for medical dressing and preparation method thereof - Google Patents
Bacterial cellulose composite membrane for medical dressing and preparation method thereof Download PDFInfo
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- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
- A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
- A61L15/18—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing inorganic materials
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- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
- A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
- A61L15/22—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing macromolecular materials
- A61L15/28—Polysaccharides or their derivatives
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- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
- A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
- A61L15/42—Use of materials characterised by their function or physical properties
- A61L15/44—Medicaments
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- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
- A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
- A61L15/42—Use of materials characterised by their function or physical properties
- A61L15/46—Deodorants or malodour counteractants, e.g. to inhibit the formation of ammonia or bacteria
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- C08J2405/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2401/00 or C08J2403/00
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- C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
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- C08K3/00—Use of inorganic substances as compounding ingredients
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- C08K3/042—Graphene or derivatives, e.g. graphene oxides
Abstract
The invention discloses a bacterial cellulose composite membrane for medical dressing and a preparation method thereof, wherein the composite membrane is prepared from a pretreatment membrane and a silver nitrate solution, the prepared composite membrane is soaked in the silver nitrate solution, and then ultraviolet reduction is carried out by ultraviolet lamp irradiation to generate nano silver particles, so that the antibacterial performance of the composite membrane is further improved; the pretreatment membrane comprises the following raw materials: 10-15 parts of modified chitosan microspheres, 15-28 parts of modified bacterial cellulose, 10-12 parts of acrylamide, 6-12 parts of N, N-methylene bisacrylamide, 2-5 parts of ammonium persulfate, 7-10 parts of sodium alginate, 4-6 parts of calcium chloride and 6-9 parts of collagen. The invention has reasonable component design and simple process operation, not only effectively realizes the preparation of the bacterial cellulose membrane, but also has excellent antibacterial performance and excellent mechanical property, can be applied to the fields of medical treatment, biology and the like, and has wide application prospect.
Description
Technical Field
The invention relates to the technical field of medical dressings, in particular to a bacterial cellulose composite membrane for medical dressings and a preparation method thereof.
Background
Bacterial Cellulose (BC) is a porous, reticulated, nanoscale biopolymer synthesized by microbial fermentation, and is named as bacterial cellulose because it is synthesized by bacteria. The fiber diameter is between 0.01 and 0.10 mu m, and is 2 to 3 orders of magnitude smaller than that of plant cellulose (10 mu m), and each filamentous fiber is of a net structure formed by a certain amount of ultramicrofibers and mainly has the difference from the plant cellulose that the filamentous fiber does not contain hemicellulose, lignin and the like. As a novel nano material, bacterial cellulose has been applied to various fields such as textile, medical materials, food and the like, and has become an international research hotspot.
The bacterial cellulose has high water holding capacity, good air permeability, good biocompatibility and better mechanical property, and has wide application prospect in the medical dressing industry. However, the existing bacterial cellulose has a single structure, poor functionality and poor antibacterial performance, which brings inconvenience to the research of people.
Aiming at the problem, a bacterial cellulose composite membrane for medical dressing and a preparation method thereof are designed, which are one of the technical problems to be solved urgently.
Disclosure of Invention
The invention aims to provide a bacterial cellulose composite membrane for medical dressings and a preparation method thereof, and aims to solve the problems in the prior art.
In order to achieve the purpose, the invention provides the following technical scheme:
a bacterial cellulose composite membrane for medical dressings is prepared from a pretreatment membrane and a silver nitrate solution.
According to an optimized technical scheme, the pretreatment membrane comprises the following raw materials: 10-15 parts of modified chitosan microspheres, 15-28 parts of modified bacterial cellulose, 10-12 parts of acrylamide, 6-12 parts of N, N-methylene bisacrylamide, 2-5 parts of ammonium persulfate, 7-10 parts of sodium alginate, 4-6 parts of calcium chloride and 6-9 parts of collagen.
According to an optimized technical scheme, the modified chitosan microsphere is prepared by modifying a chitosan microsphere and a modifier, wherein the modifier comprises sodium hydroxide, chloroacetic acid and isopropanol.
According to an optimized technical scheme, the chitosan microsphere comprises the following raw materials: 10-25 parts of chitosan, 8-12 parts of polyvinyl alcohol, 20-30 parts of silver nitrate solution, 5-9 parts of graphene oxide solution, 4-8 parts of cross-linking agent and 20-30 parts of sodium thiosulfate.
According to an optimized technical scheme, the modified bacterial cellulose is prepared from bacterial cellulose and sodium periodate.
The invention discloses a bacterial cellulose composite membrane for medical dressing and a preparation method thereof, wherein the composite membrane is prepared from a pretreatment membrane and a silver nitrate solution, the prepared composite membrane is soaked in the silver nitrate solution, and then ultraviolet reduction is carried out by ultraviolet lamp irradiation to generate nano silver particles, so that the antibacterial performance of the composite membrane is further improved.
The pretreatment membrane comprises modified chitosan microspheres, modified bacterial cellulose, acrylamide, N-methylene bisacrylamide, ammonium persulfate and other components, wherein the modified chitosan microspheres are prepared by modifying the chitosan microspheres, when the chitosan microspheres are prepared, silver ions are used as a template agent, chitosan and graphene oxide are used as bifunctional monomers, and the chitosan microspheres are prepared through the steps of eluting, drying and the like.
According to the invention, the graphene oxide is added into the chitosan microsphere, a large number of active groups such as carboxyl, hydroxyl and the like exist on the surface of the graphene oxide, and the silver ion adsorption performance of the microsphere can be improved by matching with the chitosan, meanwhile, due to the existence of the graphene oxide, the mechanical property of the pretreatment film is improved, and the adsorption selectivity to silver ions is also improved; after the chitosan microsphere is prepared, carboxymethyl groups are introduced into chitosan molecules through a modifier, so that the chitosan molecules are subjected to carboxymethyl modification, and the modified chitosan can be further crosslinked with graphene oxide; the modified nano-cellulose can be crosslinked with components such as carboxymethyl modified chitosan liquid, collagen and the like to mutually form a crosslinked network, namely a pretreatment membrane.
The bacterial cellulose is prepared by inoculating a seed culture solution with an acetobacter xylinum strain.
According to an optimized technical scheme, the preparation method of the bacterial cellulose composite membrane for the medical dressing comprises the following steps:
1) preparing materials:
2) preparing modified bacterial cellulose:
3) preparing chitosan microspheres:
a) taking chitosan, and dissolving the chitosan in acetic acid to obtain a chitosan acetic acid solution; dissolving polyvinyl alcohol in deionized water to obtain a polyvinyl alcohol aqueous solution;
b) mixing and stirring a chitosan acetic acid solution and a polyvinyl alcohol aqueous solution at room temperature, stirring, dripping a silver nitrate solution under a dark condition, stirring, slowly dripping a graphene oxide solution, continuously stirring, adding a cross-linking agent after stirring, and reacting to obtain a material A;
c) taking the material A, naturally drying at room temperature, then placing in a drying oven, drying, washing with water, then placing in sodium thiosulfate for elution, washing with water and drying to obtain chitosan microspheres;
4) taking chitosan microspheres and isopropanol prepared in the step 1), stirring, adding sodium hydroxide, continuously stirring, heating to 60-65 ℃, adding chloroacetic acid in batches, reacting to obtain a mixed solution, adjusting the pH, washing and drying to obtain modified chitosan microspheres;
5) mixing and stirring acrylamide, N-methylene bisacrylamide and ammonium persulfate, adding the prepared modified bacterial cellulose, standing for 24-26h, heating to 60-65 ℃, reacting for 5-6h, adding a sodium alginate solution, standing for 6-7d at 80-85 ℃, and adding calcium chloride to obtain a material B;
6) dissolving collagen with deionized water, stirring at 45-50 ℃ until the system is uniform, carrying out constant-temperature water bath for 1-1.5h, adding the material B, stirring at constant temperature, adding modified bacterial cellulose, continuously stirring, adding modified chitosan microspheres, carrying out ultrasonic dispersion, carrying out suction filtration, washing and drying to obtain a pretreatment membrane;
7) and (3) placing the pretreatment membrane in a silver nitrate solution, oscillating for 14-16h at 40-50 ℃, cleaning, and then placing under an ultraviolet lamp for irradiating for 1-2h to obtain the composite membrane.
The optimized technical scheme comprises the following steps:
1) preparing materials:
a) weighing bacterial cellulose, sodium periodate, chitosan, polyvinyl alcohol, silver nitrate solution, graphene oxide solution, a cross-linking agent, sodium thiosulfate, isopropanol, sodium hydroxide and chloroacetic acid in proportion for later use;
b) weighing acrylamide, N-methylene bisacrylamide, ammonium persulfate, sodium alginate, calcium chloride and collagen according to a proportion for later use; the method comprises the following steps of 1) preparing raw materials, so that subsequent operation is facilitated;
2) preparing modified bacterial cellulose:
3) preparing chitosan microspheres:
a) taking chitosan, and dissolving the chitosan in acetic acid to obtain a chitosan acetic acid solution; dissolving polyvinyl alcohol in deionized water to obtain a polyvinyl alcohol aqueous solution;
b) mixing and stirring a chitosan acetic acid solution and a polyvinyl alcohol aqueous solution at room temperature for 20-30min, dropwise adding a silver nitrate solution under a dark condition, stirring for 20-30min, slowly dropwise adding a graphene oxide solution, continuously stirring for 25-40min, adding a cross-linking agent after stirring, and reacting for 1-2h to obtain a material A; in the step 2), a silver nitrate solution is used as a template agent, chitosan is used as a functional monomer, the chitosan microspheres are self-assembled, graphene oxide is added, and at the moment, hydroxyl on the surface of the graphene oxide is matched with hydroxyl on the surface of the chitosan to be respectively coordinated with silver ions, so that an imprinted polymer is formed;
c) naturally drying the material A at room temperature, then placing in a drying oven at 60-70 ℃, drying for 30-35min, washing after drying, then placing in sodium thiosulfate for elution, wherein the elution time is 4-5h, washing for 2-3 times, and drying to obtain chitosan microspheres; in the step c), sodium thiosulfate is used as an eluent to elute silver ions on the surface of the imprinted polymer, and due to the addition of graphene oxide, the prepared chitosan has excellent mechanical properties, and the adsorbability and selectivity for the silver ions are improved;
4) taking chitosan microspheres and isopropanol prepared in the step 1), stirring for 10-25min, adding sodium hydroxide, continuing stirring for 10-15min, heating to 60-65 ℃, adding chloroacetic acid in batches at intervals of 4-6min, reacting to obtain a mixed solution, adjusting the pH to 7, washing and drying to obtain modified chitosan microspheres; in the step 4), carboxymethyl modification is carried out on the chitosan microspheres by using solutions such as isopropanol, sodium hydroxide and the like, and the modified chitosan can be combined with graphene oxide in a system to enable the chitosan microspheres to be mutually crosslinked; meanwhile, after carboxymethyl modification, the modified chitosan has better binding performance with other components (components such as bacterial cellulose and collagen) and higher compatibility;
5) mixing and stirring acrylamide, N-methylene-bisacrylamide and ammonium persulfate for 20-30min, adding the prepared modified bacterial cellulose, standing for 24-26h, heating to 60-65 ℃, reacting for 5-6h, adding a sodium alginate solution, standing for 6-7d at 80-85 ℃, and adding calcium chloride to obtain a material B; in the step 5), modified bacterial cellulose is used as a matrix, and a free radical polymerization method is utilized to prepare a modified bacterial cellulose/acrylamide interpenetrating double-crosslinked network which can be used as a matrix of a pretreatment membrane and can be crosslinked with subsequently added components such as collagen, modified chitosan microspheres and the like to form the pretreatment membrane;
6) dissolving collagen with deionized water, stirring at 45-50 ℃ until the system is uniform, carrying out constant-temperature water bath for 1-1.5h, adding the material B, stirring at constant temperature for 20-30min, adding modified bacterial cellulose, continuously stirring for 30-40min, adding modified chitosan microspheres, carrying out ultrasonic dispersion for 10-15min, carrying out suction filtration, washing and drying to obtain a pretreatment membrane;
7) placing the pretreatment membrane in a silver nitrate solution, oscillating at 40-50 ℃ for 14-16h at the oscillation speed of 100r/min, cleaning, and then placing under an ultraviolet lamp for irradiation to obtain the composite membrane. Step 7), dipping the pretreatment membrane in a silver nitrate solution, oscillating to enable silver ions to be adsorbed on the surface of the pretreatment membrane and permeate into the pretreatment membrane, and then carrying out ultraviolet reduction by using an ultraviolet lamp for irradiation, wherein the irradiation time is only 1-2h during irradiation, at the moment, the silver ions adsorbed on the surface of the pretreatment membrane are firstly reduced, and the silver ions adsorbed by the modified chitosan microspheres can form a composite membrane with the surface adsorbed nano silver ion particles, the internal nano silver particles and the unreduced silver ions doped with each other due to higher adsorption selectivity and lower reduction rate of the silver ions, so that the composite membrane has excellent antibacterial performance;
according to an optimized technical scheme, in the step 2), the preparation steps of the modified bacterial cellulose are as follows: dissolving bacterial cellulose in deionized water, stirring for 10-20min, adding sodium periodate, oxidizing at 50-60 deg.C for 6-7h, filtering, washing, and drying to obtain modified bacterial cellulose.
According to an optimized technical scheme, in the step 7), the irradiation time of the ultraviolet lamp is 1-2 h.
Compared with the prior art, the invention has the beneficial effects that:
the invention discloses a bacterial cellulose composite membrane for medical dressing and a preparation method thereof, the component design is reasonable, the process operation is simple, the preparation of the bacterial cellulose membrane is effectively realized, the bacterial cellulose membrane has excellent antibacterial performance, the bacterial cellulose membrane has excellent mechanical property, the bacterial cellulose membrane can be applied to the fields of medical treatment, biology and the like, and can also be used as a raw material of medical dressing, the application prospect is wide, and the practicability is higher.
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:
s1: preparing materials:
weighing bacterial cellulose, sodium periodate, chitosan, polyvinyl alcohol, silver nitrate solution, graphene oxide solution, a cross-linking agent, sodium thiosulfate, isopropanol, sodium hydroxide and chloroacetic acid in proportion for later use;
weighing acrylamide, N-methylene bisacrylamide, ammonium persulfate, sodium alginate, calcium chloride and collagen according to a proportion for later use;
s2: preparing modified bacterial cellulose:
dissolving bacterial cellulose in deionized water, stirring for 10min, adding sodium periodate, oxidizing at 50 ℃ for 6h, filtering, washing and drying to obtain the modified bacterial cellulose.
: preparing chitosan microspheres:
taking chitosan, and dissolving the chitosan in acetic acid to obtain a chitosan acetic acid solution; dissolving polyvinyl alcohol in deionized water to obtain a polyvinyl alcohol aqueous solution; mixing and stirring a chitosan acetic acid solution and a polyvinyl alcohol aqueous solution at room temperature for 20min, dropwise adding a silver nitrate solution under a dark condition, stirring for 20min, slowly dropwise adding a graphene oxide solution, continuously stirring for 25min, adding a cross-linking agent after stirring, and reacting for 1h to obtain a material A;
naturally drying the material A at room temperature, then placing in a drying oven at 60 ℃, drying for 30min, washing after drying, then placing in sodium thiosulfate for elution, wherein the elution time is 4h, washing for 2 times, and drying to obtain chitosan microspheres;
s4: stirring chitosan microspheres and isopropanol for 10min, adding sodium hydroxide, continuously stirring for 10min, heating to 60 ℃, adding chloroacetic acid in batches at an interval of 4min, reacting to obtain a mixed solution, adjusting the pH value to 7, washing and drying to obtain modified chitosan microspheres;
s5: mixing and stirring acrylamide, N-methylene-bisacrylamide and ammonium persulfate for 20min, adding the prepared modified bacterial cellulose, standing for 24h, heating to 60 ℃, reacting for 5h, adding a sodium alginate solution, standing for 6d at 80 ℃, and adding calcium chloride to obtain a material B;
s6: dissolving collagen with deionized water, stirring at 45 ℃ until the system is uniform, carrying out constant-temperature water bath for 1h, adding the material B, stirring at constant temperature for 20min, adding modified bacterial cellulose, continuing stirring for 30min, adding modified chitosan microspheres, carrying out ultrasonic dispersion for 10min, carrying out suction filtration, washing and drying to obtain a pretreatment membrane;
s7: and (3) placing the pretreatment membrane in a silver nitrate solution, oscillating at 40 ℃ for 14h at the oscillation speed of 100r/min, cleaning, and then placing under an ultraviolet lamp for irradiation for 1h to obtain the composite membrane.
In this embodiment, the composite membrane is prepared from a pretreatment membrane and a silver nitrate solution. The pretreatment membrane comprises the following raw materials: by weight, 10 parts of modified chitosan microspheres, 15 parts of modified bacterial cellulose, 10 parts of acrylamide, 6 parts of N, N-methylene bisacrylamide, 2 parts of ammonium persulfate, 7 parts of sodium alginate, 4 parts of calcium chloride and 6 parts of collagen.
Wherein the chitosan microsphere comprises the following raw materials: by weight, 10 parts of chitosan, 8 parts of polyvinyl alcohol, 20 parts of silver nitrate solution, 5 parts of graphene oxide solution, 4 parts of cross-linking agent and 20 parts of sodium thiosulfate.
Example 2:
s1: preparing materials:
weighing bacterial cellulose, sodium periodate, chitosan, polyvinyl alcohol, silver nitrate solution, graphene oxide solution, a cross-linking agent, sodium thiosulfate, isopropanol, sodium hydroxide and chloroacetic acid in proportion for later use;
weighing acrylamide, N-methylene bisacrylamide, ammonium persulfate, sodium alginate, calcium chloride and collagen according to a proportion for later use;
s2: preparing modified bacterial cellulose:
dissolving bacterial cellulose in deionized water, stirring for 15min, adding sodium periodate, oxidizing at 55 ℃ for 6.5h, filtering, washing and drying to obtain the modified bacterial cellulose.
: preparing chitosan microspheres:
taking chitosan, and dissolving the chitosan in acetic acid to obtain a chitosan acetic acid solution; dissolving polyvinyl alcohol in deionized water to obtain a polyvinyl alcohol aqueous solution; mixing and stirring a chitosan acetic acid solution and a polyvinyl alcohol aqueous solution at room temperature for 25min, dripping a silver nitrate solution under a dark condition, stirring for 25min, slowly dripping a graphene oxide solution, continuously stirring for 35min, adding a cross-linking agent after stirring, and reacting for 1.5h to obtain a material A;
naturally drying the material A at room temperature, then placing in a 65 ℃ drying oven, drying for 33min, washing after drying, then placing in sodium thiosulfate for elution, wherein the elution time is 4.5h, washing for 3 times, and drying to obtain chitosan microspheres;
s4: taking chitosan microspheres and isopropanol, stirring for 18min, adding sodium hydroxide, continuously stirring for 13min, heating to 63 ℃, adding chloroacetic acid in batches at an interval of 5min, reacting to obtain a mixed solution, adjusting the pH value to 7, washing and drying to obtain modified chitosan microspheres;
s5: mixing and stirring acrylamide, N-methylene-bisacrylamide and ammonium persulfate for 25min, adding the prepared modified bacterial cellulose, standing for 25h, heating to 63 ℃, reacting for 5.5h, adding a sodium alginate solution, standing for 6.5d at 83 ℃, and adding calcium chloride to obtain a material B;
s6: dissolving collagen with deionized water, stirring at 48 ℃ until the system is uniform, carrying out constant-temperature water bath for 1.3h, adding the material B, stirring at constant temperature for 25min, adding modified bacterial cellulose, continuously stirring for 35min, adding modified chitosan microspheres, carrying out ultrasonic dispersion for 12min, carrying out suction filtration, washing and drying to obtain a pretreatment membrane;
s7: and (3) placing the pretreatment membrane in a silver nitrate solution, oscillating at 45 ℃ for 15h at the oscillation speed of 100r/min, cleaning, and then placing under an ultraviolet lamp for irradiation for 1.5h to obtain the composite membrane.
In this embodiment, the composite membrane is prepared from a pretreatment membrane and a silver nitrate solution. The pretreatment membrane comprises the following raw materials: by weight, 12 parts of modified chitosan microspheres, 20 parts of modified bacterial cellulose, 11 parts of acrylamide, 10 parts of N, N-methylene bisacrylamide, 4 parts of ammonium persulfate, 9 parts of sodium alginate, 5 parts of calcium chloride and 7 parts of collagen.
Wherein the chitosan microsphere comprises the following raw materials: 19 parts of chitosan, 10 parts of polyvinyl alcohol, 25 parts of silver nitrate solution, 6 parts of graphene oxide solution, 6 parts of cross-linking agent and 25 parts of sodium thiosulfate.
Example 3:
s1: preparing materials:
weighing bacterial cellulose, sodium periodate, chitosan, polyvinyl alcohol, silver nitrate solution, graphene oxide solution, a cross-linking agent, sodium thiosulfate, isopropanol, sodium hydroxide and chloroacetic acid in proportion for later use;
weighing acrylamide, N-methylene bisacrylamide, ammonium persulfate, sodium alginate, calcium chloride and collagen according to a proportion for later use;
s2: preparing modified bacterial cellulose:
dissolving bacterial cellulose in deionized water, stirring for 20min, adding sodium periodate, oxidizing at 60 ℃ for 7h, filtering, washing and drying to obtain the modified bacterial cellulose.
: preparing chitosan microspheres:
taking chitosan, and dissolving the chitosan in acetic acid to obtain a chitosan acetic acid solution; dissolving polyvinyl alcohol in deionized water to obtain a polyvinyl alcohol aqueous solution; mixing and stirring a chitosan acetic acid solution and a polyvinyl alcohol aqueous solution at room temperature for 30min, dropwise adding a silver nitrate solution under a dark condition, stirring for 30min, slowly dropwise adding a graphene oxide solution, continuously stirring for 40min, adding a cross-linking agent after stirring, and reacting for 2h to obtain a material A;
naturally drying the material A at room temperature, then placing in a drying oven at 70 ℃, drying for 35min, washing with water after drying, then placing in sodium thiosulfate for elution, wherein the elution time is 5h, washing with water for 3 times, and drying to obtain chitosan microspheres;
s4: stirring chitosan microspheres and isopropanol for 25min, adding sodium hydroxide, continuously stirring for 15min, heating to 65 ℃, adding chloroacetic acid in batches at an interval of 6min, reacting to obtain a mixed solution, adjusting the pH value to 7, washing and drying to obtain modified chitosan microspheres;
s5: mixing and stirring acrylamide, N-methylene-bisacrylamide and ammonium persulfate for 30min, adding the prepared modified bacterial cellulose, standing for 26h, heating to 65 ℃, reacting for 6h, adding a sodium alginate solution, standing for 7d at 85 ℃, and adding calcium chloride to obtain a material B;
s6: dissolving collagen with deionized water, stirring at 45-50 ℃ until the system is uniform, carrying out constant-temperature water bath for 1.5h, adding the material B, stirring at constant temperature for 30min, adding modified bacterial cellulose, continuing stirring for 40min, adding modified chitosan microspheres, carrying out ultrasonic dispersion for 15min, carrying out suction filtration, washing and drying to obtain a pretreatment membrane;
s7: and (3) placing the pretreatment membrane in a silver nitrate solution, oscillating at 50 ℃ for 16h at the oscillation speed of 100r/min, cleaning, and then placing under an ultraviolet lamp for irradiation for 2h to obtain the composite membrane.
In this embodiment, the composite membrane is prepared from a pretreatment membrane and a silver nitrate solution. The pretreatment membrane comprises the following raw materials: by weight, 15 parts of modified chitosan microspheres, 28 parts of modified bacterial cellulose, 12 parts of acrylamide, 12 parts of N, N-methylene bisacrylamide, 5 parts of ammonium persulfate, 10 parts of sodium alginate, 6 parts of calcium chloride and 9 parts of collagen.
Wherein the chitosan microsphere comprises the following raw materials: by weight, 25 parts of chitosan, 12 parts of polyvinyl alcohol, 30 parts of silver nitrate solution, 9 parts of graphene oxide solution, 8 parts of cross-linking agent and 30 parts of sodium thiosulfate.
Detection experiment: antibacterial Performance test (Escherichia coli and Staphylococcus aureus)
1. The composite membranes prepared in the examples 1-3 are respectively cut into round pieces with the diameter of 6mm, sterilized at 120 ℃ for 20min, then the samples are pasted on the surface of a plate culture medium, and then the plate is placed in a biochemical incubator to be cultured at 37 ℃ for 24h, and the antibacterial performance of the samples is tested.
And (4) conclusion: after testing, the composite membranes prepared in examples 1-3 generate obvious inhibition zones in escherichia coli and staphylococcus aureus, and the diameter of the inhibition zone is larger than 1 mm.
The composite membrane prepared in the embodiment 1-3 was put in the bacterial liquid with the concentration of Escherichia coli of 5.2 × 105CFU/ml and the concentration of Staphylococcus aureus of 9.8 × 105CFU/ml for 24h, and the antibacterial rate was calculated respectively.
And (4) conclusion: the invention realizes the preparation of the bacterial cellulose membrane, and the bacterial cellulose membrane has excellent antibacterial performance, can be applied to the fields of medical treatment, biology and the like, can also be used as a raw material of medical dressing, has wide application prospect and higher practicability.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Claims (9)
1. A bacterial cellulose composite membrane for medical dressing which characterized in that: the composite membrane is prepared from a pretreatment membrane and a silver nitrate solution.
2. A bacterial cellulose composite membrane for medical dressings as claimed in claim 1, wherein: the pretreatment membrane comprises the following raw materials: 10-15 parts of modified chitosan microspheres, 15-28 parts of modified bacterial cellulose, 10-12 parts of acrylamide, 6-12 parts of N, N-methylene bisacrylamide, 2-5 parts of ammonium persulfate, 7-10 parts of sodium alginate, 4-6 parts of calcium chloride and 6-9 parts of collagen.
3. A bacterial cellulose composite membrane for medical dressings as claimed in claim 2, wherein: the modified chitosan microsphere is prepared by modifying a chitosan microsphere and a modifier, wherein the modifier comprises sodium hydroxide, chloroacetic acid and isopropanol.
4. A bacterial cellulose composite membrane for medical dressings as claimed in claim 3, wherein: the chitosan microsphere comprises the following raw materials: 10-25 parts of chitosan, 8-12 parts of polyvinyl alcohol, 20-30 parts of silver nitrate solution, 5-9 parts of graphene oxide solution, 4-8 parts of cross-linking agent and 20-30 parts of sodium thiosulfate.
5. A bacterial cellulose composite membrane for medical dressings as claimed in claim 2, wherein: the modified bacterial cellulose is prepared from bacterial cellulose and sodium periodate.
6. A preparation method of a bacterial cellulose composite membrane for medical dressing is characterized by comprising the following steps: the method comprises the following steps:
1) preparing materials:
2) preparing modified bacterial cellulose:
3) preparing chitosan microspheres:
a) taking chitosan, and dissolving the chitosan in acetic acid to obtain a chitosan acetic acid solution; dissolving polyvinyl alcohol in deionized water to obtain a polyvinyl alcohol aqueous solution;
b) mixing and stirring a chitosan acetic acid solution and a polyvinyl alcohol aqueous solution at room temperature, stirring, dripping a silver nitrate solution under a dark condition, stirring, slowly dripping a graphene oxide solution, continuously stirring, adding a cross-linking agent after stirring, and reacting to obtain a material A;
c) taking the material A, naturally drying at room temperature, then placing in a drying oven, drying, washing with water, then placing in sodium thiosulfate for elution, washing with water and drying to obtain chitosan microspheres;
4) taking chitosan microspheres and isopropanol prepared in the step 1), stirring, adding sodium hydroxide, continuously stirring, heating to 60-65 ℃, adding chloroacetic acid in batches, reacting to obtain a mixed solution, adjusting the pH, washing and drying to obtain modified chitosan microspheres;
5) mixing and stirring acrylamide, N-methylene bisacrylamide and ammonium persulfate, adding the prepared modified bacterial cellulose, standing for 24-26h, heating to 60-65 ℃, reacting for 5-6h, adding a sodium alginate solution, standing for 6-7d at 80-85 ℃, and adding calcium chloride to obtain a material B;
6) dissolving collagen with deionized water, stirring at 45-50 ℃ until the system is uniform, carrying out constant-temperature water bath for 1-1.5h, adding the material B, stirring at constant temperature, adding modified bacterial cellulose, continuously stirring, adding modified chitosan microspheres, carrying out ultrasonic dispersion, carrying out suction filtration, washing and drying to obtain a pretreatment membrane;
7) and (3) placing the pretreatment membrane in a silver nitrate solution, oscillating for 14-16h at 40-50 ℃, cleaning, and then placing under an ultraviolet lamp for irradiating for 1-2h to obtain the composite membrane.
7. The preparation method of the bacterial cellulose composite membrane for the medical dressing according to claim 6, wherein the preparation method comprises the following steps: the method comprises the following steps:
1) preparing materials:
a) weighing bacterial cellulose, sodium periodate, chitosan, polyvinyl alcohol, silver nitrate solution, graphene oxide solution, a cross-linking agent, sodium thiosulfate, isopropanol, sodium hydroxide and chloroacetic acid in proportion for later use;
b) weighing acrylamide, N-methylene bisacrylamide, ammonium persulfate, sodium alginate, calcium chloride and collagen according to a proportion for later use;
2) preparing modified bacterial cellulose:
3) preparing chitosan microspheres:
a) taking chitosan, and dissolving the chitosan in acetic acid to obtain a chitosan acetic acid solution; dissolving polyvinyl alcohol in deionized water to obtain a polyvinyl alcohol aqueous solution;
b) mixing and stirring a chitosan acetic acid solution and a polyvinyl alcohol aqueous solution at room temperature for 20-30min, dropwise adding a silver nitrate solution under a dark condition, stirring for 20-30min, slowly dropwise adding a graphene oxide solution, continuously stirring for 25-40min, adding a cross-linking agent after stirring, and reacting for 1-2h to obtain a material A;
c) naturally drying the material A at room temperature, then placing in a drying oven at 60-70 ℃, drying for 30-35min, washing after drying, then placing in sodium thiosulfate for elution, wherein the elution time is 4-5h, washing for 2-3 times, and drying to obtain chitosan microspheres;
4) taking chitosan microspheres and isopropanol prepared in the step 1), stirring for 10-25min, adding sodium hydroxide, continuing stirring for 10-15min, heating to 60-65 ℃, adding chloroacetic acid in batches at intervals of 4-6min, reacting to obtain a mixed solution, adjusting the pH to 7, washing and drying to obtain modified chitosan microspheres;
5) mixing and stirring acrylamide, N-methylene-bisacrylamide and ammonium persulfate for 20-30min, adding the prepared modified bacterial cellulose, standing for 24-26h, heating to 60-65 ℃, reacting for 5-6h, adding a sodium alginate solution, standing for 6-7d at 80-85 ℃, and adding calcium chloride to obtain a material B;
6) dissolving collagen with deionized water, stirring at 45-50 ℃ until the system is uniform, carrying out constant-temperature water bath for 1-1.5h, adding the material B, stirring at constant temperature for 20-30min, adding modified bacterial cellulose, continuously stirring for 30-40min, adding modified chitosan microspheres, carrying out ultrasonic dispersion for 10-15min, carrying out suction filtration, washing and drying to obtain a pretreatment membrane;
7) placing the pretreatment membrane in a silver nitrate solution, oscillating at 40-50 ℃ for 14-16h at the oscillation speed of 100r/min, cleaning, and then placing under an ultraviolet lamp for irradiation to obtain the composite membrane.
8. The preparation method of the bacterial cellulose composite membrane for the medical dressing according to claim 7, wherein the preparation method comprises the following steps: in the step 2), the preparation of the modified bacterial cellulose comprises the following steps: dissolving bacterial cellulose in deionized water, stirring for 10-20min, adding sodium periodate, oxidizing at 50-60 deg.C for 6-7h, filtering, washing, and drying to obtain modified bacterial cellulose.
9. The preparation method of the bacterial cellulose composite membrane for the medical dressing according to claim 7, wherein the preparation method comprises the following steps: in the step 7), the irradiation time of the ultraviolet lamp is 1-2 h.
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