CN113136044A - Fibroin oxidizing bacterial cellulose nano composite film and preparation method thereof - Google Patents
Fibroin oxidizing bacterial cellulose nano composite film and preparation method thereof Download PDFInfo
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Abstract
The invention provides a fibroin oxidized bacteria cellulose nano composite film and a preparation method thereof, wherein the fibroin oxidized bacteria cellulose nano composite film comprises fibroin, nano silver, polyvinyl alcohol and oxidized bacteria cellulose, the fibroin oxidized bacteria cellulose contains a three-dimensional net-shaped structure, the three-dimensional net-shaped structure is a net-shaped structure formed by the bacteria cellulose, the nano silver is attached to the three-dimensional net-shaped structure formed by the oxidized bacteria cellulose, and the composite film is formed by casting. The film prepared by the invention can be applied to the fields of storage packaging materials and biomedical materials, and the preparation method is simple, mild in condition, convenient to operate, easy to control, free of adding a cross-linking agent and suitable for quantitative production.
Description
Technical Field
The invention relates to the technical field of textile materials, and particularly relates to a fibroin oxidizing bacteria cellulose nano composite film 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, which is a regenerative natural protein extracted from silkworm cocoons, has good physical, chemical, biological and optical properties, has been processed into different forms such as films, nanofibers, gels, 3D materials, particles and microneedles, and is widely used in the fields of biology, medicine, electronics, optics, filtration, and the like, but pure silk fibroin films are hard and brittle when dried, and are easily broken, thereby limiting the wide application thereof.
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. Cellulose Nanofibers (CNFs) have the advantages of wide sources, low cost, biodegradability, uniform dispersion in a biopolymer matrix, and the like, have good barrier property, transparency and higher mechanical and thermal properties, and are one of the most promising nano-reinforcing materials. Bacterial Cellulose (BC) is an important source for obtaining Cellulose nanofibers as a biopolymer produced by gluconobacter xylosus. Compared with cellulose nanofiber extracted from wood, the bacterial cellulose nanofiber has higher crystallinity, purity, mechanical strength, polymerization degree and biocompatibility. After bacterial cellulose is oxidized by 2,2,6, 6-tetramethylpiperidine-1-oxyl (TEMPO), a large number of carboxyl groups can be introduced on the surface of the cellulose fiber, the electrostatic repulsion among the fibers enables the diameter and the length of the bacterial cellulose to be more uniformly distributed, and the oxidized bacterial cellulose is used as an effective reinforcing filler in a polymer composite material at present.
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. The silk fibroin contains 18 amino acids, wherein tyrosine and the like have stronger polarity, so that the silk fibroin has electron donating capability, and therefore, the silk fibroin can be used as a reducing agent and a stabilizing agent for synthesizing nano silver.
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.
Disclosure of Invention
The technical problem to be solved is as follows: the technical problem to be solved by the invention is to provide a fibroin oxidizing bacteria cellulose nano composite film, which is prepared by taking a regenerated fibroin aqueous solution as a reducing agent and a stabilizing agent, assisting ultraviolet irradiation to synthesize nano silver, taking oxidized bacteria cellulose nano fibers as a reinforcing nano material, taking polyvinyl alcohol as a plasticizer and adopting a solution casting method.
The technical scheme is as follows: the utility model provides a fibroin oxidation bacterial cellulose nanometer complex film, fibroin oxidation bacterial cellulose nanometer complex film includes silk fibroin, nano-silver, polyvinyl alcohol and oxidation bacterial cellulose, fibroin oxidation bacterial cellulose contains three-dimensional network structure, three-dimensional network structure is the network structure of bacterial cellulose formation, nano-silver is attached to on the three-dimensional network structure of oxidation bacterial cellulose formation, the complex film is through the casting film.
A preparation method of a fibroin oxidizing bacteria cellulose nano composite film comprises the following steps:
s1, preparing a silk fibroin/nano silver colloidal solution: adding silver nitrate into regenerated silk fibroin aqueous solution with a certain concentration, uniformly mixing and stirring to obtain silk fibroin/silver nitrate mixed solution, then carrying out ultraviolet irradiation on the mixed solution and cooperatively stirring to form silk fibroin/nano silver colloidal solution;
s2, preparing oxidizing 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;
s3, preparing a fibroin oxidizing bacteria cellulose nano composite film: 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 carrying out tape casting on the mixed solution in a flat-bottom vessel by adopting a solution pouring method, and drying to form the nano composite membrane.
Preferably, the regenerated silk fibroin aqueous solution in the step S1 is a regenerated silk fibroin aqueous solution prepared by dissolving degummed silk fibroin with a calcium chloride ternary system solution and dialyzing; the concentration of the regenerated silk fibroin aqueous solution is 2 wt%, and the material-liquid ratio of the silver nitrate to the regenerated silk fibroin aqueous solution is 4 mg: 1 mL.
Preferably, the irradiation intensity of the UV light irradiation of the mixed solution in the step S1 is 200-2The wavelength is 250-300 nm.
Preferably, the concentration of the bacterial cellulose homogenate in the step S2 is 0.1-0.15 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 cosolvent in step S3 is glycerol, and the mass of the glycerol is 5-8 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 S3 is 1-7 wt% of the sum of dry weight of the silk fibroin and the polyvinyl alcohol
Has the advantages that: the fibroin oxidizing bacteria cellulose nano composite film 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 fibroin oxidized bacterial cellulose nano composite membrane is prepared by a solution casting method, the oxidized bacterial cellulose keeps a mesh structure of the bacterial cellulose, has higher length-diameter ratio, is suitable for being used as a natural reinforced nano material, and replaces a cross-linking agent in the prior art by adding polyvinyl alcohol, on the basis of no addition of a cross-linking agent, the rupture strength and tensile modulus of the oxidized bacterial cellulose/silk fibroin/polyvinyl alcohol/nano silver composite membrane are remarkably improved compared with those of the oxidized bacterial cellulose/silk fibroin/polyvinyl alcohol/nano silver composite membrane before compounding, the mechanical property of the composite membrane is improved due to the reinforcing effect of the oxidized bacterial cellulose, and rigid nano silver is more uniformly distributed due to the addition of the oxidized bacterial cellulose. The oxidized bacterial cellulose is uniformly distributed in silk fibroin and polyvinyl alcohol matrixes, and the nano silver is fixed by virtue of a net structure of the oxidized bacterial cellulose, so that the dispersibility of the nano silver in the composite membrane is improved, better load transfer and interfibrillar sliding can be realized, and the mechanical property is greatly improved;
2. the maximum thermal decomposition temperature of the fibroin oxidized bacterial cellulose nano composite membrane prepared by the invention can reach 310.5 ℃, the composite membrane still has higher thermal stability, simultaneously, with the increase of the content of the oxidized bacterial cellulose, the free hydrophilic carboxylate radical on the oxidized bacterial cellulose macromolecule is increased therewith, compared with the fibroin/polyvinyl alcohol composite membrane, the hydrophilic performance of the fibroin oxidized bacterial cellulose nano composite membrane is improved, the water vapor barrier property is slightly reduced with the increase of the content of the oxidized bacterial cellulose, but the higher water vapor barrier property can still be maintained, and the use requirements of materials such as packaging, wound dressing and the like can be completely met;
3. the fibroin oxidizing bacteria cellulose nano composite membrane prepared by the invention can block 99.99% of ultraviolet light, aromatic amino acid in fibroin can absorb ultraviolet light below 300nm, nano silver dispersed in a polymer matrix prevents the transmission of the ultraviolet light and improves along with the increase of the content of the oxidizing bacteria cellulose, and the addition of the oxidizing bacteria cellulose further increases the dispersibility of the nano silver, so that the composite membrane has a better ultraviolet shielding effect;
4. the nano silver in the fibroin oxidized bacterial cellulose nano composite membrane prepared by the invention can inhibit the growth of escherichia coli and wilting disease in corn, the antibacterial activity of the composite membrane is not influenced by the compounding of the oxidized bacterial cellulose, and the fibroin/polyvinyl alcohol/nano silver/oxidized bacterial cellulose composite membrane has better antibacterial property;
5. the preparation method disclosed by the invention is simple, mild in condition, convenient to operate, easy to control, free of adding a cross-linking agent, suitable for quantitative production, and very suitable for the fields of storage packaging materials and biomedical materials.
Description of the drawings:
the accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this application, illustrate embodiment(s) of the invention and together with the description serve to explain the principles of the invention:
FIG. 1 is a flow chart of the preparation of a fibroin oxidizing bacterial cellulose nano composite membrane;
FIG. 2 is a transmission electron micrograph of bacterial cellulose and TEMPO oxidized bacterial cellulose, in which: (a) bacterial cellulose, (b) TEMPO oxidized bacterial cellulose;
FIG. 3 is a scanning electron micrograph of several different composite films, in which: (a) silk fibroin/polyvinyl alcohol, (b) silk fibroin/polyvinyl alcohol/nano silver, (c) silk fibroin/polyvinyl alcohol/nano silver/3% oxidized bacterial cellulose, (d) silk fibroin/polyvinyl alcohol/nano silver/7% oxidized bacterial cellulose; the silk fibroin/polyvinyl alcohol/nano silver/7% oxidized bacterial cellulose composite membrane comprises the following components in percentage by weight: (e) X-ray energy spectrum, (f) silver element profile;
FIG. 4 is a transmission electron micrograph of several different composite films, in which: (a) silk fibroin/polyvinyl alcohol/nano silver, (b) silk fibroin/polyvinyl alcohol/nano silver/7% oxidized bacterial cellulose;
fig. 5 shows the thermal stability of the fibroin oxidizing bacterial cellulose nanocomposite membrane, wherein: (a) thermogram, (b) microperimetric thermogravimetric analysis curve;
FIG. 6 shows the ultraviolet resistance of the fibroin oxidizing bacteria cellulose nano composite membrane: (a) ultraviolet light transmittance, and (b) the influence of the content of the oxidized bacterial cellulose on the ultraviolet shielding performance.
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
A preparation method of a fibroin oxidizing bacteria cellulose nano composite film 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-liquid ratio of the silver nitrate to the regenerated silk fibroin aqueous solution is 4 mg: 1mL, mixing and stirring to obtain silk fibroin/silver nitrate mixed solution, and irradiating with 200 w/hr2Ultraviolet irradiation with the wavelength of 300nm 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, the TEMPO, sodium bromide and sodium hypochlorite is 0.2:0.2:0.65:43.75, uniformly mixing, and centrifuging to remove supernatant liquid to obtain wet TEMPO oxidized bacterial cellulose;
s3, preparing a fibroin oxidizing bacteria cellulose nano composite film: mixing silk fibroin/nano silver colloidal solution and polyvinyl alcohol solution, adding glycerol, wherein 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 wet TEMPO oxidized bacterial cellulose solution, wherein the mass of the oxidized bacterial cellulose is 1 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
A preparation method of a fibroin oxidizing bacteria cellulose nano composite film 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-liquid ratio of the silver nitrate to the regenerated silk fibroin aqueous solution is 4 mg: 1mL, mixing and stirring to obtain silk fibroin/silver nitrate mixed solution, and irradiating with 200 w/hr2Ultraviolet irradiation with the wavelength of 300nm 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 0.15 wt% of bacterial cellulose homogenate, adding a TEMPO/NaBr/NaClO mixed oxidation system into the bacterial cellulose homogenate, wherein the mass ratio of the bacterial cellulose, the TEMPO, sodium bromide and sodium hypochlorite is 0.3:0.2:0.85:38.15, uniformly mixing, and centrifuging to remove supernatant to obtain wet TEMPO oxidized bacterial cellulose;
s3, preparing a fibroin oxidizing bacteria cellulose nano composite film: mixing silk fibroin/nano silver colloidal solution and polyvinyl alcohol solution, adding glycerol, wherein the mass of the glycerol is 8 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 1 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 3
A preparation method of a fibroin oxidizing bacteria cellulose nano composite film 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-liquid ratio of the silver nitrate to the regenerated silk fibroin aqueous solution is 4 mg: 1mL, mixing and stirring to obtain silk fibroin/silver nitrate mixed solution, and irradiating the mixed solution with an irradiation intensity of 300 w/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 0.1 wt% of bacterial cellulose homogenate, 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 0.29075:0.1072:0.7572:40.956, uniformly mixing, and centrifuging to remove supernatant to obtain wet TEMPO oxidized bacterial cellulose;
s3, preparing a fibroin oxidizing bacteria cellulose nano composite film: 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 7 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 4
A preparation method of a fibroin oxidizing bacteria cellulose nano composite film 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-liquid ratio of the silver nitrate to the regenerated silk fibroin aqueous solution is 4 mg: 1mL, evenly mixing and stirring to obtain a silk fibroin/silver nitrate mixed solution, and then irradiating the mixed solution with the intensity300 w-2Ultraviolet 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 0.1 wt% of bacterial cellulose homogenate, 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 0.29075:0.1072:0.7572:40.956, uniformly mixing, and centrifuging to remove supernatant to obtain wet TEMPO oxidized bacterial cellulose;
s3, preparing a fibroin oxidizing bacteria cellulose nano composite film: 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-bottomed container by adopting a solution casting method, and drying to form the nano composite membrane.
Example 5
A preparation method of a fibroin oxidizing bacteria cellulose nano composite film 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-liquid ratio of the silver nitrate to the regenerated silk fibroin aqueous solution is 4 mg: 1mL, mixing and stirring to obtain silk fibroin/silver nitrate mixed solution, and irradiating the mixed solution with an irradiation intensity of 300 w/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 0.1 wt% of bacterial cellulose homogenate, 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 0.29075:0.1072:0.7572:40.956, uniformly mixing, and centrifuging to remove supernatant to obtain wet TEMPO oxidized bacterial cellulose;
s3, preparing a fibroin oxidizing bacteria cellulose nano composite film: 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 6
A preparation method of a fibroin oxidizing bacteria cellulose nano composite film 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-liquid ratio of the silver nitrate to the regenerated silk fibroin aqueous solution is 4 mg: 1mL, mixing and stirring to obtain silk fibroin/silver nitrate mixed solution, and irradiating the mixed solution with an irradiation intensity of 300 w/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 0.1 wt% of bacterial cellulose homogenate, 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 0.29075:0.1072:0.7572:40.956, uniformly mixing, and centrifuging to remove supernatant to obtain wet TEMPO oxidized bacterial cellulose;
s3, preparing a fibroin oxidizing bacteria cellulose nano composite film: 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 7 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.
And (3) 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 fibroin oxidizing bacteria cellulose nano composite membrane are measured on an American Instron 5545 type universal material testing machine provided with a 100N sensor, the composite membrane 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 average value is taken to obtain the mechanical property indexes of the composite membrane, such as a stress-strain curve, the breaking strength, the stretching modulus, the breaking elongation and the like;
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.
From the table above, it can be seen that the mechanical properties of the fibroin oxidizing bacterial cellulose nano composite film prepared by the invention are remarkably improved under the condition that a certain amount of oxidizing bacterial cellulose is added; when the composite membrane contains the oxidized bacterial cellulose, compared with a silk fibroin/polyvinyl alcohol composite membrane, the hydrophilic performance of the silk fibroin oxidized bacterial cellulose nano composite membrane is slightly improved, the water vapor transmission rate is increased along with the increase of the content of the oxidized bacterial cellulose, and the use requirements of materials such as packaging materials, wound dressings and the like can be completely met; compared with silk fibroin/polyvinyl alcohol/nano silver films, the antibacterial activity of the composite film is not influenced by the addition of the oxidized bacterial cellulose.
As can be seen by combining the scanning electron microscope photograph of fig. 3 and the projection electron microscope photograph of fig. 4, the nano silver can be uniformly distributed in the composite film, and the three-dimensional network structure can be clearly seen along with the increase of the content of the oxidized bacterial fibers; in combination with the fig. 5, the silk fibroin/polyvinyl alcohol/nano silver/oxidized bacteria cellulose composite membrane still has higher thermal stability, and can completely meet the use requirements of materials such as packaging, wound dressing and the like;
finally, as shown in FIG. 6, the ultraviolet shielding efficiency of the fibroin oxidized bacteria cellulose nano composite membrane is improved with the increase of the content of oxidized bacteria cellulose, and the composite membrane can block 99.97-99.99% of UV-B (280-315nm) and 99.17-99.97% 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. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.
Claims (8)
1. The utility model provides a fibroin oxidation bacterial cellulose nanometer complex film, its characterized in that, fibroin oxidation bacterial cellulose nanometer complex film includes silk fibroin, nano-silver, polyvinyl alcohol and oxidation bacterial cellulose, fibroin oxidation bacterial cellulose contains three-dimensional network structure, three-dimensional network structure is the network structure of bacterial cellulose formation, nano-silver is attached to on the three-dimensional network structure of oxidation bacterial cellulose formation, the complex film is through the casting film.
2. A preparation method of a fibroin oxidizing bacteria cellulose nano composite film is characterized by comprising the following steps:
s1, preparing a silk fibroin/nano silver colloidal solution: adding silver nitrate into regenerated silk fibroin aqueous solution with a certain concentration, uniformly mixing and stirring to obtain silk fibroin/silver nitrate mixed solution, then carrying out ultraviolet irradiation on the mixed solution and cooperatively stirring to form silk fibroin/nano silver colloidal solution;
s2, preparing oxidizing 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;
s3, preparing a fibroin oxidizing bacteria cellulose nano composite film: 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 carrying out tape casting on the mixed solution in a flat-bottom vessel by adopting a solution pouring method, and drying to form the nano composite membrane.
3. The preparation method of the fibroin oxidizing bacteria cellulose nano-composite membrane according to claim 2, characterized in that: the regenerated silk fibroin aqueous solution in the step S1 is a regenerated silk fibroin aqueous solution prepared by dissolving degummed silk fibroin by a calcium chloride ternary system solution and dialyzing; the concentration of the regenerated silk fibroin aqueous solution is 2 wt%, and the material-liquid ratio of the silver nitrate to the regenerated silk fibroin aqueous solution is 4 mg: 1 mL.
4. Fibroin oxidizing bacterial fiber according to claim 2The preparation method of the plain nano composite film is characterized by comprising the following steps: the irradiation intensity of the mixed solution in the step S1 with UV light irradiation is 200-2The wavelength is 250-300 nm.
5. The preparation method of the fibroin oxidizing bacteria cellulose nano-composite membrane according to claim 2, characterized in that: the concentration of the bacterial cellulose homogenate in the step S2 is 0.1-0.15 wt%.
6. The preparation method of the fibroin oxidizing bacteria cellulose nano-composite membrane according to claim 2, characterized in that: 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.
7. The preparation method of the fibroin oxidizing bacteria cellulose nano-composite membrane according to claim 2, characterized in that: in the step S3, the cosolvent is glycerol, and the mass of the glycerol is 5-8 wt% of the total dry weight of the silk fibroin and the polyvinyl alcohol.
8. The preparation method of the fibroin oxidizing bacteria cellulose nano-composite membrane according to claim 2, characterized in that: the mass of the oxidized bacterial cellulose in the step S3 is 1-7 wt% of the sum of dry weight of the silk fibroin and the polyvinyl alcohol.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114656737A (en) * | 2022-03-10 | 2022-06-24 | 盐城工业职业技术学院 | Oxidized bacterial cellulose reinforced fibroin antibacterial nano composite material and preparation method thereof |
| 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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2021
- 2021-04-23 CN CN202110439855.4A patent/CN113136044A/en not_active Withdrawn
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114656737A (en) * | 2022-03-10 | 2022-06-24 | 盐城工业职业技术学院 | Oxidized bacterial cellulose reinforced fibroin antibacterial nano composite material and preparation method thereof |
| 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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