CN114656737A - Oxidized bacterial cellulose reinforced fibroin antibacterial nano composite material and preparation method thereof - Google Patents
Oxidized bacterial cellulose reinforced fibroin antibacterial nano composite material and preparation method thereof Download PDFInfo
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- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
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- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 7
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
- C08L29/02—Homopolymers or copolymers of unsaturated alcohols
- C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L89/00—Compositions of proteins; Compositions of derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0806—Silver
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides an oxidized bacterial cellulose reinforced fibroin antibacterial nano composite material and a preparation method thereof. The invention prepares the antibacterial nano composite material of oxidized bacterial cellulose enhanced fibroin by compounding regenerated silk fibroin, nano silver and oxidized bacterial cellulose nano fibers, taking polyvinyl alcohol as a plasticizer and adopting a solution casting method.
Description
Technical Field
The invention relates to the technical field of textile materials, in particular to an oxidized bacterial cellulose reinforced fibroin antibacterial nano composite material and a preparation method thereof.
Background
Nowadays, with the increasing concern of environmental problems, in order to reduce or even replace the traditional petroleum-based composite materials, the development of multifunctional bionic nano composite materials by utilizing renewable resources gradually becomes a research hotspot.
Silk fibroin is derived from arthropods such as spiders, silkworms, bees, and the like, and is widely studied for its excellent physicochemical properties and biological activity. Silk fibroin is approved by the U.S. Food and Drug Administration (FDA) for use in certain medical products. Silk is mainly composed of silk fibroin and sericin. Wherein the silk fibroin is positioned in the core region of the silk fiber and consists of a light chain and a heavy chain; while sericin is coated on the silk fibroin chains. Silk fibers contain about 70-75% silk fibroin and 25-30% sericin. Typically, to reduce immune rejection, sericin is often degummed to remove sericin in applications. The silk fibroin has good physical and chemical properties and biological activity, such as mechanical strength, biocompatibility, non-toxicity, biodegradability and the like. The research on tissue repair by compounding silk fibroin and other materials is increasing year by year, and the application prospect is strong. However, pure silk fibroin films are hard and brittle when dried and are easily broken, which limits their wide application.
The natural reinforcing nano-filler and the antibacterial nano-particles are added into the biopolymer, so that the biological nano-composite material with improved mechanical properties and antibacterial activity can be developed. Silver Nanoparticles (AgNPs) have been widely used in biomedical and active packaging materials due to their broad-spectrum antibacterial properties and high antibacterial efficiency. At present, methods for synthesizing nano silver include chemical methods, physical methods, biological methods and the like, wherein the method for synthesizing nano silver by using natural polymers as reducing agents and stabilizing agents has the advantages of simple operation, ecological friendliness, low cost, no toxicity and the like, and is becoming a new breakthrough of nano silver production technology. At present, there are research reports that fibroin and bacterial cellulose are used as raw materials, the functions of fibroin and bacterial cellulose are combined to prepare a composite membrane with excellent performance, whether a crosslinking agent is added or not is discussed in the reports to influence the physical and chemical properties of a nano bacterial cellulose/fibroin compound, the results show that the surface of the membrane added with the crosslinking agent group is relatively flat, the structure is obviously changed, and mechanical strength tests show that the elongation at break of the oxidized bacterial cellulose/fibroin without the crosslinking agent and the oxidized bacterial cellulose/fibroin with the crosslinking agent are relatively good, the mechanical property of the latter is excellent, and the two have significant difference. The composite membrane prepared by adding the cross-linking agent has better performance, and has certain prospect in the aspect of medical materials, particularly in the aspect of cellularized vascular stents. Therefore, materials prepared from the bacterial cellulose and the fibroin at present contain chemical cross-linking agents, and the existence of the chemical cross-linking agents can affect the biocompatibility of the bacterial cellulose and fibroin composite material, cause hidden danger to the safety performance of the biological material, and affect the green, environment-friendly and safe performance of the material. Therefore, the preparation of the fibroin oxidized bacterial cellulose membrane with high environmental protection safety and high strength is particularly important. The experimental group used regenerated silk fibroin aqueous solution as a reducing agent and a stabilizing agent, assisted by ultraviolet irradiation to synthesize nano-silver, oxidized bacterial cellulose nano-fiber as a reinforced nano-material and polyvinyl alcohol as a plasticizer, and prepared the fibroin oxidized bacterial cellulose nano-composite membrane by a solution casting method, but the performance of the fibroin oxidized bacterial cellulose nano-composite membrane is unstable due to the fact that the nano-silver particles are reduced by ultraviolet irradiation in the preparation process.
Disclosure of Invention
The technical problem to be solved is as follows: the technical problem to be solved by the invention is to provide an oxidized bacterial cellulose reinforced fibroin antibacterial nano composite material, wherein regenerated silk fibroin, nano silver and oxidized bacterial cellulose nano fibers are compounded, polyvinyl alcohol is used as a plasticizer, and the oxidized bacterial cellulose reinforced fibroin antibacterial nano composite material is prepared by a solution casting method.
The technical scheme is as follows: an antibacterial nano composite material of oxidized bacterial cellulose reinforced fibroin is prepared by mixing silk fibroin, nano silver, polyvinyl alcohol and oxidized bacterial cellulose.
A preparation method of an oxidized bacterial cellulose reinforced fibroin antibacterial nano composite material is provided, wherein the composite material is prepared by one of the following methods:
the first method,
S1, preparing a regenerated silk protein aqueous solution: dissolving degummed fibroin by a calcium chloride ternary system solution, and dialyzing to obtain a regenerated silk protein aqueous solution;
s2, carrying Ag+Preparing oxidized bacterial cellulose: will be provided withPretreating bacterial cellulose to obtain bacterial cellulose homogenate, adding a TEMPO/NaBr/NaClO mixed oxidation system into the bacterial cellulose homogenate, uniformly mixing, centrifuging to remove supernatant to obtain wet TEMPO oxidized bacterial cellulose, adding the wet TEMPO oxidized bacterial cellulose into a silver nitrate solution, fully and uniformly stirring, and filtering to obtain the Ag-loaded silver nitrate solution+Oxidizing the bacterial cellulose;
s3, preparing silver-loaded oxidized bacterial cellulose: will carry Ag+Adding the oxidized bacterial cellulose into the amino modified polyvinyl alcohol solution, and reacting to obtain silver-loaded oxidized bacterial cellulose sol;
s4, preparing the oxidized bacterial cellulose reinforced fibroin antibacterial nano composite material: mixing the regenerated silk protein aqueous solution and the polyvinyl alcohol solution, adding a cosolvent, uniformly mixing and stirring, adding silver-loaded oxidized bacteria cellulose sol, treating to obtain a mixed solution, casting the mixed solution in a flat-bottomed container by adopting a solution casting method, and drying to form a nano composite membrane;
or the second way,
a. Preparing silk fibroin/nano silver colloidal solution;
b. preparing oxidized bacterial cellulose: pretreating bacterial cellulose to obtain bacterial cellulose homogenate, then adding a TEMPO/NaBr/NaClO mixed oxidation system into the bacterial cellulose homogenate, uniformly mixing, and centrifuging to remove supernatant to obtain wet TEMPO oxidized bacterial cellulose;
c. preparing an oxidized bacterial cellulose reinforced fibroin antibacterial nano composite material: mixing silk fibroin/nano silver colloidal solution and polyvinyl alcohol solution, adding cosolvent, mixing and stirring uniformly, adding wet TEMPO oxidized bacterial cellulose solution, carrying out ultrasonic treatment in an ice bath environment to obtain mixed solution, casting the mixed solution in a flat-bottom vessel by adopting a solution casting method, and drying to form the nano composite material;
in the second mode, the silk fibroin/nano silver colloid is prepared by adopting one of the following methods:
method A, dissolving degummed fibroin in calcium chloride ternary system solutionHydrolyzing and dialyzing to obtain regenerated silk fibroin aqueous solution, concentrating to concentration of 2 wt%, adding silver nitrate, mixing and stirring uniformly to obtain silk fibroin/silver nitrate mixed solution, wherein the material-liquid ratio of silver nitrate to the regenerated silk fibroin aqueous solution is 4 mg: 1mL, then performing ultraviolet irradiation on the mixed solution, stirring in a matching manner, and performing irradiation at an irradiation intensity of 200-2The wavelength is 250-300nm to form silk fibroin/nano-silver colloidal solution;
or the method B, dissolving the degummed silk fibroin by formate solution, adding silver nitrate, wherein the mass ratio of the silver nitrate to the silk fibroin is 0.2-0.5: 1, dialyzing by using deionized water, stirring while dialyzing, and irradiating by using ultraviolet rays to form silk fibroin/nano silver colloidal solution.
Preferably, the regenerated aqueous fibroin solution of the step S1 has a concentration of 2 wt%.
Preferably, the concentration of the bacterial cellulose homogenate in the step S2 is 0.1-0.2 wt%.
Preferably, the mass ratio of the bacterial cellulose, TEMPO, sodium bromide and sodium hypochlorite in the step S2 is 0.2-0.3:0.1-0.2:0.65-0.85: 38.15-43.75.
Preferably, the concentration of the amino modified polyvinyl alcohol solution in step S3 is 0.5-10 wt%, wherein the preparation method of the amino modified polyvinyl alcohol solution is as follows:
c. adding succinic anhydride and triethylamine into a polyvinyl alcohol solution, and reacting to obtain a polyvinyl alcohol solution modified by succinic anhydride;
d. adding EDC and NHS into the modified polyvinyl alcohol solution, adding an amino-terminated hyperbranched polymer after reaction, and reacting to obtain amino-modified polyvinyl alcohol.
Preferably, the mass ratio of the succinic anhydride, the triethylamine, the polyvinyl alcohol, the EDC, the NHS and the amino-terminated hyperbranched polymer is 5: 1: 40: 10: 5: 20.
Preferably, the cosolvent in step S4 is glycerol, and the mass of the glycerol is 3-7.5 wt% of the sum of dry weights of the silk fibroin and the polyvinyl alcohol.
Preferably, the mass of the oxidized bacterial cellulose in the step S4 is 1-7 wt% of the sum of dry weights of the silk fibroin and the polyvinyl alcohol. Has the beneficial effects that: the oxidized bacterial cellulose reinforced fibroin antibacterial nano composite material and the preparation method thereof have the following advantages:
1. the invention prepares the oxidized bacterial cellulose by oxidizing the bacterial cellulose by a TEMPO/NaClO/NaBr system, takes the oxidized bacterial cellulose as a reinforced nano material, the oxidized bacterial cellulose reinforced silk protein antibacterial nano composite material is prepared by a solution casting method, the first preparation method of the invention is different from the second preparation method, the regenerated silk protein aqueous solution is not adopted as a reducing agent and a stabilizing agent in the invention, the nano silver is synthesized by ultraviolet irradiation, the silver is directly and creatively adsorbed on the surface of the oxidized bacterial cellulose in a soaking adsorption mode, the nano silver can be positioned and generated and captured inside by utilizing the amino-terminated hyperbranched polymer, after the polyvinyl alcohol is grafted with the amino-terminated hyperbranched compound, the bacterial cellulose is further oxidized to enhance the fibroin antibacterial nano composite material, so that the mechanical property of the composite material is improved;
2. according to the invention, the nano silver is attached to the surface of the oxidized bacterial cellulose, the amino modified polyvinyl alcohol adhesive is adopted, and the polyvinyl alcohol is also used as a plasticizer, so that the dispersibility of the oxidized bacterial cellulose in the silk fibroin matrix is improved, and the adhesive and the plasticizer are both polyvinyl alcohol, so that the compatibility is high, and the environment is protected;
3. the method II of the preparation method of the invention adopts two different methods to prepare the silk fibroin/nano silver colloidal solution, wherein one method adopts the traditional ternary solution method to prepare the silk fibroin aqueous solution, the silk fibroin/nano silver colloidal solution is generated by mixing with silver nitrate, the other method adopts a formate dissolving system, silver nitrate is directly added for dialysis, because the molecular weight of the silk fibroin is larger in the formate dissolving system and the gel is easy to generate in the dialysis process, the physical action reduces the gel phenomenon while dialyzing, and high-content silver nitrate is added to prevent the concentration of the silver nitrate from reducing due to the dialysis in the dialysis process and cannot participate in the ultraviolet illumination to synthesize the nano silver, the molecular weight of the silk fibroin/nano silver colloidal solution prepared by the method is larger, the mechanical property of the material formed in the later period is better;
4. the oxidized bacterial cellulose reinforced fibroin antibacterial nano composite material prepared by the invention can block 99.99% of ultraviolet light and has a higher ultraviolet resistance effect;
5. compared with the prior art, the antibacterial nano composite material of oxidized bacterial cellulose reinforced fibroin prepared by the invention has higher antibacterial property;
6. the preparation method disclosed by the invention is simple, mild in condition, stable in performance, free of adding a cross-linking agent, suitable for quantitative production, and very suitable for the fields of storage packaging materials and biomedical materials.
Detailed Description
The present invention will be described in detail with reference to specific embodiments, which are illustrative of the invention and are not to be construed as limiting the invention.
Example 1
The preparation method of the oxidized bacterial cellulose reinforced fibroin antibacterial nano composite material comprises the following steps:
s1, preparing a silk fibroin/nano silver colloidal solution: adding silver nitrate into a regenerated silk fibroin aqueous solution with the concentration of 2 wt%, wherein the feed-to-liquid ratio of the silver nitrate to the regenerated silk fibroin aqueous solution is 4 mg: 1mL, uniformly mixing and stirring to obtain a silk fibroin/silver nitrate mixed solution, and then irradiating the mixed solution with the irradiation intensity of 300w for a time of hr/m2Ultraviolet irradiation with the wavelength of 250nm is carried out and is matched with stirring to form silk fibroin/nano silver colloidal solution;
s2, preparing oxidizing bacterial cellulose: pretreating bacterial cellulose to obtain bacterial cellulose homogenate with the concentration of 0.1 wt%, then adding a TEMPO/NaBr/NaClO mixed oxidation system into the bacterial cellulose homogenate, wherein the mass ratio of the bacterial cellulose to the TEMPO to the sodium bromide to the sodium hypochlorite is 0.2: 0.1: 0.65: 40, uniformly mixing, and centrifuging to remove supernatant liquid to obtain wet TEMPO oxidized bacterial cellulose;
s3, preparing the oxidized bacterial cellulose reinforced fibroin antibacterial nano composite material: mixing silk fibroin/nano silver colloidal solution and polyvinyl alcohol solution, adding glycerol, wherein the mass of the glycerol is 6 wt% of the total dry weight of the silk fibroin and the polyvinyl alcohol, uniformly mixing and stirring, adding wet TEMPO oxidized bacterial cellulose solution, wherein the mass of the oxidized bacterial cellulose is 5 wt% of the total dry weight of the silk fibroin and the polyvinyl alcohol, carrying out ultrasonic treatment in an ice bath environment to obtain mixed solution, finally casting the mixed solution in a flat-bottomed container by adopting a solution casting method, and drying to form the nano composite membrane.
Example 2
The preparation method of the oxidized bacterial cellulose reinforced fibroin antibacterial nano composite material comprises the following steps:
s1, preparing a silk fibroin/nano silver colloidal solution: dissolving degummed silk fibroin with calcium formate and calcium chloride solution, adding silver nitrate into the degummed silk fibroin with the mass ratio of calcium chloride being 6: 1, the mass ratio of silver nitrate to silk fibroin being 0.2-0.5: 1, dialyzing with deionized water, stirring while dialyzing, irradiating with ultraviolet light with the irradiation intensity of 300 w-2The wavelength is 250nm, and silk fibroin/nano-silver colloid solution is formed;
s2, preparing oxidizing bacterial cellulose: pretreating bacterial cellulose to obtain bacterial cellulose homogenate with the concentration of 0.1 wt%, then adding a TEMPO/NaBr/NaClO mixed oxidation system into the bacterial cellulose homogenate, wherein the mass ratio of the bacterial cellulose to the TEMPO to the sodium bromide to the sodium hypochlorite is 0.2: 0.1: 0.65: 40, uniformly mixing, and centrifuging to remove supernatant liquid to obtain wet TEMPO oxidized bacterial cellulose;
s3, preparing the oxidized bacterial cellulose reinforced fibroin antibacterial nano composite material: mixing silk fibroin/nano-silver colloidal solution and polyvinyl alcohol solution, adding glycerol, wherein the mass of the glycerol is 6 wt% of the total dry weight of the silk fibroin and the polyvinyl alcohol, uniformly mixing and stirring, adding wet TEMPO oxidized bacterial cellulose solution, wherein the mass of the oxidized bacterial cellulose is 3 wt% of the total dry weight of the silk fibroin and the polyvinyl alcohol, carrying out ultrasonic treatment in an ice bath environment to obtain mixed solution, finally casting the mixed solution in a flat-bottom vessel by adopting a solution pouring method, and drying to form the nano-composite membrane.
Example 3
The preparation method of the oxidized bacterial cellulose reinforced fibroin antibacterial nano composite material comprises the following steps:
s1, preparing a regenerated silk protein aqueous solution: dissolving degummed fibroin by a calcium chloride ternary system solution, dialyzing to obtain a regenerated silk protein aqueous solution, and concentrating the water-soluble concentration of the regenerated silk protein to 2 wt%;
s2, carrying Ag+Preparing oxidized bacterial cellulose: pretreating bacterial cellulose to obtain bacterial cellulose homogenate with the concentration of 0.1 wt%, then adding a TEMPO/NaBr/NaClO mixed oxidation system into the bacterial cellulose homogenate, uniformly mixing, centrifuging and removing supernatant to obtain wet TEMPO oxidized bacterial cellulose, wherein the mass ratio of the bacterial cellulose, TEMPO, sodium bromide and sodium hypochlorite is 0.2: 0.1: 0.65: 43.75, adding the wet TEMPO oxidized bacterial cellulose into a silver nitrate solution, fully and uniformly stirring, and filtering to obtain the Ag-loaded silver nitrate solution+Oxidizing the bacterial cellulose;
s3, preparing silver-loaded oxidized bacterial cellulose: will carry Ag+Adding the oxidized bacterial cellulose into 0.5 wt% amino modified polyvinyl alcohol solution, and reacting to obtain silver-loaded oxidized bacterial cellulose sol;
s4, preparing the oxidized bacterial cellulose reinforced fibroin antibacterial nano composite material: mixing a regenerated silk fibroin aqueous solution and a polyvinyl alcohol solution, adding a cosolvent, wherein the cosolvent is glycerol, the mass of the glycerol is 5 wt% of the total dry weight of the silk fibroin and the polyvinyl alcohol, uniformly mixing and stirring, adding silver-loaded oxidized bacteria cellulose sol, the mass of the silver-loaded oxidized bacteria cellulose is 0.5 wt% of the total dry weight of the silk fibroin and the polyvinyl alcohol, processing to obtain a mixed solution, casting the mixed solution in a flat-bottom container by adopting a solution casting method, and drying to form a nano composite membrane;
the preparation method of the amino-modified polyvinyl alcohol solution in step S3 includes:
e. adding succinic anhydride and triethylamine into a polyvinyl alcohol solution, and reacting to obtain a polyvinyl alcohol solution modified by succinic anhydride;
adding EDC and NHS into the modified polyvinyl alcohol solution, adding an amino-terminated hyperbranched polymer after reaction, and reacting to obtain amino-modified polyvinyl alcohol, wherein the mass ratio of succinic anhydride, triethylamine, polyvinyl alcohol, EDC, NHS and the amino-terminated hyperbranched polymer is 5: 1: 40: 10: 5: 20.
Example 4
The preparation method of the oxidized bacterial cellulose reinforced fibroin antibacterial nano composite material comprises the following steps:
s1, preparing a regenerated silk protein aqueous solution: dissolving degummed fibroin by a calcium chloride ternary system solution, dialyzing to obtain a regenerated silk protein aqueous solution, and concentrating the water-soluble concentration of the regenerated silk protein to 2 wt%;
s2, carrying Ag+Preparing oxidized bacterial cellulose: pretreating bacterial cellulose to obtain bacterial cellulose homogenate with the concentration of 0.2 wt%, then adding a TEMPO/NaBr/NaClO mixed oxidation system into the bacterial cellulose homogenate, uniformly mixing, centrifuging and removing supernatant to obtain wet TEMPO oxidized bacterial cellulose, wherein the mass ratio of the bacterial cellulose, TEMPO, sodium bromide and sodium hypochlorite is 0.3: 0.2: 0.85:38.15, adding the wet TEMPO oxidized bacterial cellulose into a silver nitrate solution, fully and uniformly stirring, and filtering to obtain the Ag-loaded bacterial cellulose+Oxidizing the bacterial cellulose;
s3, preparing silver-loaded oxidized bacterial cellulose: will carry Ag+Adding the oxidized bacterial cellulose into 10 wt% amino modified polyvinyl alcohol solution, and reacting to obtain silver-loaded oxidized bacterial cellulose sol;
s4, preparing the oxidized bacterial cellulose reinforced fibroin antibacterial nano composite material: mixing a regenerated silk fibroin aqueous solution and a polyvinyl alcohol solution, adding a cosolvent, wherein the cosolvent is glycerol, the mass of the glycerol is 7.5 wt% of the total dry weight of the silk fibroin and the polyvinyl alcohol, uniformly mixing and stirring, adding silver-loaded oxidized bacteria cellulose sol, the mass of the silver-loaded oxidized bacteria cellulose is 5 wt% of the total dry weight of the silk fibroin and the polyvinyl alcohol, processing to obtain a mixed solution, casting the mixed solution in a flat-bottom container by adopting a solution casting method, and drying to form a nano composite membrane;
the preparation method of the amino-modified polyvinyl alcohol solution in step S3 includes:
f. adding succinic anhydride and triethylamine into a polyvinyl alcohol solution, and reacting to obtain a polyvinyl alcohol solution modified by succinic anhydride;
adding EDC and NHS into the modified polyvinyl alcohol solution, adding an amino-terminated hyperbranched polymer after reaction, and reacting to obtain amino-modified polyvinyl alcohol, wherein the mass ratio of succinic anhydride, triethylamine, polyvinyl alcohol, EDC, NHS and the amino-terminated hyperbranched polymer is 5: 1: 40: 10: 5: 20.
And (4) performance testing:
and (3) testing mechanical properties: according to the standard of ASTM D882-02 test method for tensile properties of plastic sheet materials, the mechanical properties of the oxidized bacterial cellulose reinforced fibroin antibacterial nanocomposite are measured on an American Instron 5545 type universal material testing machine equipped with a 100N sensor, the composite film is cut into the size of 1cm multiplied by 5cm, the clamping length of a sample is 2cm, the stretching speed is 5mm/min, 5 groups of data are measured on each sample, and the mechanical property indexes such as a stress-strain curve, breaking strength, stretching modulus, breaking elongation and the like of the composite film are obtained by averaging;
water contact angle and water vapor transmission rate test: the hydrophilicity and water vapor barrier properties of the composite films were evaluated by measuring the water contact angle and water vapor transmission rate. Use of Germany
A DSA100 model droplet shape analyzer, a company, observes wetting behavior of the composite film and ultrapure water by the static drop method at room temperature, and measures a contact angle using a droplet of 10 μ L in size. Testing the water vapor transmission rate of the composite film according to modified ASTM E96/E96M-2014 standard "standard test method for water vapor permeability of materials"; and (3) testing the antibacterial performance: and (3) irradiating the composite membrane for 30min by using an ultraviolet lamp for sterilization, testing the antibacterial property of the composite membrane by using escherichia coli as a gram-negative bacteria representative and using wilting bacteria in corn as a gram-positive bacteria representative, placing a test wafer with the diameter of 0.7cm on an agar plate, placing the agar plate in a 37 ℃ incubator, incubating for 24h, and measuring the sizes of the inhibition zones of different samples.
Testing the ultraviolet shielding efficiency: the ultraviolet visible spectrophotometer tests the absorbance of the solution, the scanning range is 200-800nm, and the resolution is 2 nm.
As can be seen from the table above, the mechanical properties of the composite membrane are remarkably improved when a certain amount of the oxidized bacterial cellulose is added into the oxidized bacterial cellulose reinforced fibroin antibacterial nano composite material prepared by the invention; the mechanical property of the composite membrane can be improved to a certain extent no matter what form of the oxidized bacterial cellulose is added into the silk fibroin solution, the silk fibroin aqueous solution prepared by dissolving silk fibroin by adopting a ternary solution is adopted in the embodiment 1, the mechanical property of the composite material obtained by the method is slightly lower than that of the method in the embodiments 2 and 3-4, the silk fibroin solution obtained by adopting a formate method is adopted in the embodiment 2, the silk fibroin dissolved by the method has longer molecular weight and is easy to gel in a dialysis process, so that higher content of silver nitrate is added in the dialysis process, the aim of adding higher content of silver nitrate is to ensure that the content of nano silver generated by reaction under the ultraviolet light condition is reduced by spinning the silver nitrate in the dialysis process through a dialysis bag, the method ensures the content of the nano silver, and meanwhile, the mechanical property of the composite material can be improved by the silk fibroin with higher molecular weight, as can be seen from the above table, the mechanical properties of the film prepared in the manner of example 2 are much higher than those of example 1; in the preparation method of the embodiment 3-4, silver is directly and creatively adsorbed on the surface of oxidized bacterial cellulose in a soaking adsorption mode, nano silver can be generated and captured inside by utilizing an amino-terminated hyperbranched polymer, and after the polyvinyl alcohol is grafted with the amino-terminated hyperbranched polymer, the oxidized bacterial cellulose is further used for enhancing the fibroin antibacterial nano composite material, so that the mechanical property of the composite material is improved, meanwhile, the fixation of the nano silver in the composite material is enhanced, and the antibacterial effect is improved.
When the composite material contains the oxidized bacterial cellulose, compared with a silk fibroin/polyvinyl alcohol composite membrane, the composite membrane material prepared by different methods can completely meet the use requirements of materials such as packaging, wound dressing and the like.
And finally, oxidizing the bacterial cellulose from the upper surface to enhance the ultraviolet resistance of the fibroin antibacterial nano composite material, wherein the composite film can block 99.99 percent of UV-B (280-315nm) and 99.99 percent of UV-A (315-400 nm).
The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Those skilled in the art can modify or change the above-described embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which may be made by those skilled in the art without departing from the spirit and scope of the present invention as defined in the appended claims.
Claims (9)
1. An antibacterial nano composite material of oxidized bacterial cellulose reinforced fibroin is characterized in that: the composite material is prepared by mixing silk fibroin, nano silver, polyvinyl alcohol and oxidized bacterial cellulose.
2. A preparation method of an oxidized bacterial cellulose reinforced fibroin antibacterial nano composite material is characterized in that the composite material is prepared by adopting one of the following methods:
in a first way,
S1, preparing a regenerated silk protein aqueous solution: dissolving degummed fibroin by a calcium chloride ternary system solution, and dialyzing to obtain a regenerated silk protein aqueous solution;
s2, carrying Ag+Preparing oxidized bacterial cellulose: pretreating bacterial cellulose to obtain bacterial cellulose homogenate, adding a TEMPO/NaBr/NaClO mixed oxidation system into the bacterial cellulose homogenate, mixing uniformly, centrifuging to remove supernatant to obtain wet TEMPO oxidized bacterial cellulose, adding the wet TEMPO oxidized bacterial cellulose into a silver nitrate solution, and filling the solution with silver nitrate solutionStirring evenly, filtering to obtain the Ag-carried material+Oxidizing the bacterial cellulose;
s3, preparing silver-loaded oxidized bacterial cellulose: will carry Ag+Adding the oxidized bacterial cellulose into the amino modified polyvinyl alcohol solution, and reacting to obtain silver-loaded oxidized bacterial cellulose sol;
s4, preparing the oxidized bacterial cellulose reinforced fibroin antibacterial nano composite material: mixing the regenerated silk protein aqueous solution and the polyvinyl alcohol solution, adding a cosolvent, uniformly mixing and stirring, adding silver-loaded oxidized bacteria cellulose sol, treating to obtain a mixed solution, casting the mixed solution in a flat-bottomed container by adopting a solution casting method, and drying to form a nano composite membrane;
or the second way,
a. Preparing silk fibroin/nano silver colloidal solution;
b. preparing oxidized bacterial cellulose: pretreating bacterial cellulose to obtain bacterial cellulose homogenate, then adding a TEMPO/NaBr/NaClO mixed oxidation system into the bacterial cellulose homogenate, uniformly mixing, and centrifuging to remove supernatant to obtain wet TEMPO oxidized bacterial cellulose;
c. preparing an oxidized bacterial cellulose reinforced fibroin antibacterial nano composite material: mixing silk fibroin/nano silver colloidal solution and polyvinyl alcohol solution, adding cosolvent, uniformly mixing and stirring, adding wet TEMPO oxidized bacteria cellulose solution, carrying out ultrasonic treatment in an ice bath environment to obtain a mixed solution, finally casting the mixed solution in a flat bottom vessel by adopting a solution casting method, and drying to form the nano composite material;
in the second mode, the silk fibroin/nano silver colloid is prepared by adopting one of the following methods:
the method A comprises the steps of dissolving degummed fibroin by a calcium chloride ternary system solution, dialyzing to obtain a regenerated fibroin aqueous solution, concentrating until the concentration is 2 wt%, adding silver nitrate, mixing and stirring uniformly to obtain a fibroin/silver nitrate mixed solution, wherein the material-liquid ratio of the silver nitrate to the regenerated fibroin aqueous solution is 4 mg: 1mL, then the mixed solution is irradiated by ultraviolet light and is stirred in a matching wayIllumination intensity of 200-2The wavelength is 250-300nm to form silk fibroin/nano-silver colloidal solution;
or B, dissolving degummed fibroin by formate solution, and adding silver nitrate, wherein the mass ratio of the silver nitrate to the fibroin is 0.2-0.5: and 1, dialyzing by using deionized water, stirring while dialyzing, and irradiating by using ultraviolet rays to form a silk fibroin/nano silver colloid solution.
3. The method for preparing the oxidized bacterial cellulose reinforced fibroin antibacterial nanocomposite material according to claim 2, wherein: the concentration of the regenerated silk fibroin aqueous solution in the step S1 is 2 wt%.
4. The method for preparing the oxidized bacterial cellulose reinforced fibroin antibacterial nanocomposite material according to claim 2, wherein: the concentration of the bacterial cellulose homogenate in the step S2 is 0.1-0.2 wt%.
5. The method for preparing the oxidized bacterial cellulose reinforced fibroin antibacterial nanocomposite material according to claim 2, wherein: in the step S2, the mass ratio of the bacterial cellulose to the TEMPO to the sodium bromide to the sodium hypochlorite is 0.2-0.3:0.1-0.2:0.65-0.85: 38.15-43.75.
6. The method for preparing the oxidized bacterial cellulose reinforced fibroin antibacterial nanocomposite material according to claim 2, wherein: the concentration of the amino-modified polyvinyl alcohol solution in the step S3 is 0.5-10 wt%, wherein the preparation method of the amino-modified polyvinyl alcohol solution comprises the following steps:
a. adding succinic anhydride and triethylamine into a polyvinyl alcohol solution, and reacting to obtain a polyvinyl alcohol solution modified by succinic anhydride;
b. adding EDC and NHS into the modified polyvinyl alcohol solution, adding the amino-terminated hyperbranched polymer after reaction, and reacting to obtain the amino-modified polyvinyl alcohol.
7. The method for preparing the oxidized bacterial cellulose reinforced fibroin antibacterial nanocomposite material according to claim 6, wherein: the mass ratio of the succinic anhydride, the triethylamine, the polyvinyl alcohol, the EDC, the NHS and the amino-terminated hyperbranched polymer is 5: 1: 40: 10: 5: 20.
8. the method for preparing the oxidized bacterial cellulose reinforced fibroin antibacterial nanocomposite material according to claim 2, wherein: in the step S4, the cosolvent is glycerol, and the mass of the glycerol is 3-7.5 wt% of the total dry weight of the silk fibroin and the polyvinyl alcohol.
9. The method for preparing the oxidized bacterial cellulose reinforced fibroin antibacterial nanocomposite material according to claim 2, wherein: the mass of the silver-loaded oxidized bacterial fiber in the step S4 is 0.5-5 wt% of the total dry weight of the silk fibroin and the polyvinyl alcohol.
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| CN115651233A (en) * | 2022-09-07 | 2023-01-31 | 浙江理工大学 | Preparation method of ionic electroactive driver based on carboxylated bacterial cellulose |
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| CN115368694A (en) * | 2022-09-30 | 2022-11-22 | 河北百展科技发展有限公司 | Biomass-based reinforced polyvinyl alcohol composite material and preparation method thereof |
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