CN110229384B - Silver-loaded diamidoxime cellulose/chitosan/fibroin composite aerogel and preparation method thereof - Google Patents
Silver-loaded diamidoxime cellulose/chitosan/fibroin composite aerogel and preparation method thereof Download PDFInfo
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
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- C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2301/08—Cellulose derivatives
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2405/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2401/00 or C08J2403/00
- C08J2405/08—Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
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Abstract
The invention discloses a silver-loaded diamidoxime cellulose/chitosan/fibroin composite aerogel and a preparation method thereof. Obtaining rodlike diamidoxime cellulose after modification; preparing silver-loaded bisamidoxime cellulose/chitosan composite sol by using bisamidoxime cellulose as a carrier and dialdehyde chitosan as a reducing agent and a gel component through coordination and in-situ reduction; then adding a fibroin solution with a certain concentration, wherein each component can independently form strong combination under the interaction force of static electricity, hydrogen bonds and the like; and (3) freezing and drying to obtain the silver-loaded diamidoxime cellulose/chitosan/fibroin composite aerogel. The obtained aerogel has the advantages of regular tissue structure, high porosity, good biocompatibility, high mechanical property and outstanding antibacterial effect, and is expected to be used in the fields of tissue engineering, biomedicine, medical dressing and the like.
Description
Technical Field
The invention relates to a silver-loaded diamidoxime cellulose/chitosan/fibroin composite aerogel and a preparation method thereof, belonging to the field of functional composite material science.
Background
The aerogel is a wet gel, most of solvent is removed, so that the liquid content in the gel is far less than the solid content, or the medium filled in the space network structure is gas, and the appearance of the aerogel is a solid material. The aerogel has the advantages of low density, high porosity, ultrahigh specific surface area, material transmission and the like, and therefore has wide application or potential application value in a plurality of fields such as adsorption catalysis, medical biomaterials, sound absorption and heat insulation materials, filter materials, template materials and the like. Since Tan et al (Advanced Materials,2001, 13,644-646) succeeded in preparing cellulose aerogel from cellulose derivatives in 2001, natural polymer aerogel rapidly developed into the third generation aerogel Materials, surpassing inorganic aerogel and artificially synthesized organic polymer aerogel. The aerogel building material has the characteristics of the traditional aerogel, and simultaneously integrates the excellent performances of the aerogel building material, such as low cost, good biocompatibility, biodegradability and environmental friendliness, thereby becoming the first choice of the aerogel building material.
The silk is natural filament and mainly comprises silk fibroin and sericin, wherein the silk fibroin accounts for about 70% of the total weight of the silk fibroin and is relatively easy to extract. The silk fibroin contains up to 18 different types of amino acids, wherein 8 types of amino acids are necessary for human bodies, has good physicochemical properties such as slow release property, air permeability, biocompatibility, biodegradability and the like, and can be processed to obtain regenerated silk fibroin products (such as films, powder, fibers, gel and the like) in various forms. Therefore, the composite aerogel material constructed by taking silk fibroin as a component has rapid development and wide application, and is particularly applied to the fields of tissue engineering scaffolds, cell culture substrates and the like. However, pure silk fibroin materials are highly brittle, mechanically weak, easily breakable, and have high dissolution rate, and therefore are rarely used directly.
As a natural cationic polymer, the chitosan has rich hydroxyl and amino active groups on the surface, has the characteristics of good hygroscopicity, film forming property, permeability, good biocompatibility, biodegradability and the like, is a material which is non-toxic, harmless, free of immune antigen reaction and has wide development prospect. The chitosan and the silk fibroin are compounded, so that the functions of the chitosan and the silk fibroin can be integrated, and the advantages and the disadvantages of the chitosan and the silk fibroin are made up for in performance, thereby achieving the synergistic effect.
At present, there are some reports on fibroin/chitosan composite membranes (Materials Science and Engineering C,2017,70: 736-744; Journal of biological Materials Research Part A,2018,106:397-407), but there are few reports on composite aerogels. In addition, the conventional aerogel requires high mechanical strength for the material in addition to the requirement on the compatibility among components, so that the conventional aerogel is convenient to regenerate and recycle; the functions are comprehensive, and the multifunctional electric heating cooker is more suitable for the use in the fields of high requirements, multiple functions and the like.
Disclosure of Invention
In view of the above problems, the technical object of the present invention is to provide a high-purity antibacterial composite aerogel material and a high-efficiency, simple and convenient preparation method thereof. Most of the traditional preparation methods of the composite aerogel adopt a blending sol-gel method, and nano particles are easy to exude after being doped, and have uneven load, infirm fixation and the like. The invention creatively adopts the modified amidoxime-hydroxylamine oxime cellulose as a carrier and a stabilizer, adopts dialdehyde chitosan as a reducing agent and a gel component, and loads nano silver particles in situ, thereby not only improving the fixation and dispersion of nano silver, but also avoiding the exudation of the nano silver; and blending the prepared silver-loaded diammine oxime cellulose/chitosan composite with fibroin, and freeze-drying to obtain the silver-loaded diammine oxime cellulose/chitosan/fibroin composite aerogel. The obtained aerogel can integrate functions of all components, and has good biocompatibility and biodegradability, outstanding mechanical property and antibacterial property, excellent adsorbability and recyclable regeneration capacity.
In order to achieve the technical purpose, the technical scheme provided by the invention is as follows:
the invention provides silver-loaded diamidoxime cellulose/chitosan/fibroin composite aerogel, which comprises the following components, by weight, 1-5 parts of diamidoxime cellulose, 0.05-2 parts of nano-silver, 3-7 parts of fibroin and 3-7 parts of dialdehyde chitosan.
The invention also provides a preparation method of the silver-loaded diammine oxime cellulose/chitosan/fibroin composite aerogel, which comprises the following steps:
preparation of S1 silver-carrying bisamidoxime cellulose/chitosan
Adding 0.001-0.1 mol/L silver nitrate solution into 1.5-10 wt% of amidoxime-hydroxylamine oxime cellulose dispersion according to the volume ratio of 1: 10-100: 1, and treating in an ultrasonic cell crusher with the power set at 500-1200W for 15-90 min; taking out the product, washing, centrifuging, and uniformly dispersing in fresh deionized water again, wherein the deionized water is 0.5-2 times of the diamidoxime cellulose dispersion liquid in volume; then adding 0.5-5 wt% of dialdehyde chitosan solution into a reaction system, and reacting for 0.5-6 h at 50-90 ℃ to obtain silver-loaded bisamidoxime cellulose/chitosan composite sol;
formation of S2 blend Sol
Adding a fibroin solution with the concentration of 4-15 wt% into the silver-loaded diamidoxime cellulose/chitosan composite sol according to the volume ratio of 1: 1-1: 100, and uniformly stirring to form silver-loaded diamidoxime cellulose/chitosan/fibroin blended sol;
preparation of S3 composite aerogel
And (3) ultrasonically defoaming the blended sol, injecting the blended sol into a mold, freezing the mixture at-50 ℃ for 4-10 hours, and drying to obtain the silver-loaded diamidoxime cellulose/chitosan/fibroin composite aerogel.
Further, the preparation process of the dialdehyde chitosan in the step S1 comprises the following steps: adding chitosan into an acetic acid solution with the concentration of 2 wt% according to the bath ratio of 1: 100-1: 10, and stirring until the chitosan is completely dissolved to obtain a chitosan solution; introducing nitrogen, adding a sodium periodate solution into a chitosan solution, wherein the sodium periodate is 13-66% of the chitosan by mass, oxidizing the chitosan solution at 30-60 ℃ in the dark for 1-10 h, adding ethylene glycol to stop the reaction, freeze-drying to obtain dialdehyde chitosan, and dissolving the dialdehyde chitosan in deionized water to prepare dialdehyde chitosan solutions with different concentrations.
Further, the deacetylation degree of the chitosan is 85-95%.
Further, the silk fibroin solution preparation process described in step S2 is as follows: placing raw silk into 0.3-3 wt% Na2CO3 solution according to a bath ratio of 1: 20-1: 100, treating for 30min at 95-100 ℃, circulating for three times, taking out silk fibroin fibers, cleaning, drying, placing the silk fibroin fibers into a mixed solution of CaCl2/H2O/C2H5OH with a molar ratio of 1:8:2 according to a bath ratio of 1: 10-1: 50, magnetically stirring for 2-6H at 78-88 ℃, centrifuging to remove undissolved silk fibroin fibers to obtain a light yellow silk fibroin solution, dialyzing for 24-72H, and concentrating polyethylene glycol to obtain the silk fibroin solution.
Further, the preparation step of the diamidoxime cellulose in step S1 is:
step 1, placing cellulose into a NaOH solution with the concentration of 0.5-5 wt% according to the bath ratio of 1: 100-1: 10, and boiling for 30-150 min; then, placing the mixture in 10-30 wt% NaOH solution according to the bath ratio of 1: 100-1: 10, and stirring for 30-180 min at room temperature; filtering, washing and drying to obtain the alkalized cellulose;
step 2, placing the alkalized cellulose into acetone according to a bath ratio of 1: 20-1: 50, and condensing and refluxing for 10-45 min at 50-60 ℃ under the protection of nitrogen; then adding 2-cyano-3-ethoxy ethyl acrylate, wherein the weight of the 2-cyano-3-ethoxy ethyl acrylate is 0.2-2 times that of the alkalized cellulose, magnetically stirring for 10-45 min, then adding ammonium ceric nitrate, and continuing to react for 1-8 h, wherein the ammonium ceric nitrate is 0.2-3% of the alkalized cellulose by mass; filtering the product, washing with methanol and water for several times, and drying to obtain the graft copolymer cellulose;
and 3, adding the graft copolymerization cellulose into 1mol/L hydroxylamine solution according to a bath ratio of 1: 15-1: 50, reacting for 1-6 h under the conditions of 65-75 ℃ and magnetic stirring, and sequentially carrying out methanol washing and drying on the product to obtain the diaminooxime cellulose.
Further, the cellulose is one or a mixture of two of rod-shaped microcrystalline cellulose and nano cellulose.
The invention has the beneficial effects that:
(1) the nano silver is generated on the surface of the diamidoxime cellulose in situ, and is firmly loaded in the aerogel, uniformly distributed and uniform in size.
(2) The dialdehyde chitosan is used as a reducing agent and an aerogel component, the reduction process is green and environment-friendly, and the gelation process is simple and efficient.
(3) The prepared aerogel has high purity, good biocompatibility, high mechanical strength, regular tissue structure, large pores, high component activity and outstanding antibacterial effect.
Drawings
FIG. 1 is a scanning electron microscope image of silver-loaded bisamidoxime microcrystalline cellulose;
FIG. 2 is a further enlarged scanning electron micrograph taken from FIG. 1;
FIG. 3 is a scanning electron microscope image of the Ag-loaded bisamidoxime cellulose/chitosan/fibroin composite aerogel prepared in example 1;
FIG. 4 is a diagram of the bacteriostatic effect of the fibroin/chitosan composite aerogel on Staphylococcus aureus;
fig. 5 is a graph of the bacteriostatic effect of the silver-loaded diammine oxime cellulose/chitosan/fibroin composite aerogel prepared in example 1 on staphylococcus aureus.
Detailed Description
In order to clarify the technical solution and technical object of the present invention, the present invention will be further described with reference to the accompanying drawings and specific examples.
1. Preparation of dialdehyde chitosan solution
The preparation process of the dialdehyde chitosan comprises the following steps: adding chitosan into an acetic acid solution with the concentration of 2 wt% according to the bath ratio of 1: 100-1: 10, and stirring until the chitosan is completely dissolved to obtain a chitosan solution; introducing nitrogen, adding a sodium periodate solution into a chitosan solution, wherein the sodium periodate is 13-66% of the chitosan by mass, oxidizing the chitosan solution at 30-60 ℃ in the dark for 1-10 h, adding ethylene glycol to stop the reaction, freeze-drying to obtain dialdehyde chitosan, and dissolving the dialdehyde chitosan in deionized water to obtain the dialdehyde chitosan solution.
Further, the deacetylation degree of the chitosan is 85-95%.
2. Preparation of bisaminooxime cellulose
Step 1, placing cellulose into a NaOH solution with the concentration of 0.5-5 wt% according to the bath ratio of 1: 100-1: 10, and boiling for 30-150 min; then, placing the mixture in 10-30 wt% NaOH solution according to the bath ratio of 1: 100-1: 10, and stirring for 30-180 min at room temperature; filtering, washing and drying to obtain the alkalized cellulose;
step 2, placing the alkalized cellulose into acetone according to a bath ratio of 1: 20-1: 50, and condensing and refluxing for 10-45 min at 50-60 ℃ under the protection of nitrogen; then adding 2-cyano-3-ethoxy ethyl acrylate, wherein the weight of the 2-cyano-3-ethoxy ethyl acrylate is 0.2-2 times that of the alkalized cellulose, magnetically stirring for 10-45 min, then adding ammonium ceric nitrate, and continuing to react for 1-8 h, wherein the ammonium ceric nitrate is 0.2-3% of the alkalized cellulose by mass; filtering the product, washing with methanol and water for several times, and drying to obtain the graft copolymer cellulose;
and 3, adding the graft copolymerization cellulose into 1mol/L hydroxylamine solution according to a bath ratio of 1: 15-1: 50, reacting for 1-6 h under the conditions of 65-75 ℃ and magnetic stirring, and sequentially carrying out methanol washing and drying on the product to obtain the diaminooxime cellulose.
3. Preparation of fibroin solution
The preparation process of the fibroin solution comprises the following steps: placing raw silk into 0.3-3 wt% Na2CO3 solution according to a bath ratio of 1: 20-1: 100, treating for 30min at 95-100 ℃, circulating for three times, taking out silk fibroin fibers, cleaning, drying, placing the silk fibroin fibers into a mixed solution of CaCl2/H2O/C2H5OH with a molar ratio of 1:8:2 according to a bath ratio of 1: 10-1: 50, magnetically stirring for 2-6H at 78-88 ℃, centrifuging to remove undissolved silk fibroin fibers to obtain a light yellow silk fibroin solution, dialyzing for 24-72H, and concentrating polyethylene glycol to obtain the silk fibroin solution.
Example 1:
weighing 5g of microcrystalline cellulose, placing the microcrystalline cellulose in 200mL of NaOH solution with the concentration of 1.25 wt%, and boiling for 90 min; then transferring the mixture into 120mL of NaOH solution with the concentration of 20 wt%, and stirring the mixture for 60min at room temperature; filtering, washing and drying to obtain the alkalized microcrystalline cellulose. Placing 2g of alkalized microcrystalline cellulose in 45mL of acetone, carrying out condensation reflux at 60 ℃ for 30min under the protection of nitrogen, adding 2g of 2-cyano-3-ethoxy ethyl acrylate for reaction for 10min, then adding 0.01g of ammonium ceric nitrate for reaction for 4h, filtering the product, washing with methanol, washing with deionized water, and drying to obtain the graft copolymer microcrystalline cellulose. Adding the mixture into 1mol/L hydroxylamine solution according to a bath ratio of 1:30, reacting for 3 hours under the condition of magnetic stirring at 65 ℃, washing and drying products by methanol and deionized water in sequence to prepare the diamidoxime microcrystalline cellulose;
adding 100mL of silver nitrate solution with the concentration of 0.001mol/L into 20mL of 2 wt% diamidoxime microcrystalline cellulose dispersion, and placing the mixture in a 500W ultrasonic cell crusher for treatment for 30 min; after washing and centrifuging the diamidoxime microcrystalline cellulose, re-dispersing the diamidoxime microcrystalline cellulose in 20mL of deionized water; adding 10mL of 2 wt% dialdehyde chitosan solution into the reaction system, and reacting for 3h at 75 ℃ to obtain the silver-loaded bisamidoxime microcrystalline cellulose/chitosan composite sol.
Adding 10mL of 12 wt% fibroin solution into the silver-loaded diamidoxime microcrystalline cellulose/chitosan composite sol, and uniformly stirring to form blended sol. And (3) ultrasonically defoaming the blended sol, injecting the blended sol into a mold, freezing the mixture at the temperature of-50 ℃ for 6 hours, and drying the mixture to obtain the silver-loaded diamidoxime microcrystalline cellulose/chitosan/fibroin composite aerogel.
The dialdehyde chitosan solution, the diamidooxime cellulose and the fibroin solution used in this example were prepared according to methods 1, 2 and 3, respectively, described above.
Example 2:
weighing 4g of microcrystalline cellulose, placing the microcrystalline cellulose in 100mL of NaOH solution with the concentration of 3 wt%, and boiling for 60 min; then transferring the mixture into 200mL of NaOH solution with the concentration of 15 wt%, and stirring for 45min at room temperature; filtering, washing and drying to obtain the alkalized microcrystalline cellulose. Placing 2g of alkalized microcrystalline cellulose into 50mL of acetone, carrying out condensation reflux at 50 ℃ for 15min under the protection of nitrogen, adding 1g of monomer 2-cyano-3-ethoxy ethyl acrylate for reaction for 10min, then adding 0.01g of ammonium ceric nitrate for reaction for 1h, filtering the product, washing the product with methanol, washing the product with deionized water, and drying the product to obtain the graft copolymer microcrystalline cellulose. Adding the mixture into 1mol/L hydroxylamine solution according to a bath ratio of 1:15, reacting for 4h at 70 ℃, washing products by methanol and deionized water in sequence, and drying to obtain a diamidoxime microcrystalline cellulose material;
adding 80mL of silver nitrate solution with the concentration of 0.05mol/L into 10mL of 5 wt% diaminooxime nanocellulose dispersion, and placing the mixture in an 800W ultrasonic cell crusher for treatment for 20 min; after washing and centrifuging the diamidoxime nanocellulose, re-dispersing the diamidoxime nanocellulose in 15mL of deionized water; adding 50mL of 6 wt% dialdehyde chitosan solution into the reaction system, and reacting for 4h at 60 ℃ to obtain the silver-loaded bisamidoxime nanocellulose/chitosan composite sol.
30mL of 5 wt% silk fibroin solution is added into the silver-loaded diamidoxime nanocellulose/chitosan composite sol, and the mixture is uniformly stirred to form blended sol. And (3) ultrasonically defoaming the blended sol, injecting the blended sol into a mold, freezing the mixture at-50 ℃ for 4 hours, and drying the mixture to obtain the silver-loaded diamidoxime nano-cellulose/chitosan/fibroin composite aerogel.
The dialdehyde chitosan solution, the diamidooxime cellulose and the fibroin solution used in this example were prepared according to methods 1, 2 and 3, respectively, described above.
Example 3:
weighing 3g of nano-cellulose, placing the nano-cellulose in 100mL of 2 wt% NaOH solution, and boiling for 120 min; then transferring the mixture into 150mL of NaOH solution with the concentration of 10 wt%, and stirring the mixture for 120min at room temperature; and filtering, washing and drying to obtain the alkalized nano-cellulose. Putting 2g of alkalized nano-cellulose into 75mL of acetone, and carrying out condensation reflux for 45min at 50 ℃ under the protection of nitrogen; 4g of monomer 2-cyano-3-ethoxy ethyl acrylate is added for reaction for 45min, then 0.01g of ammonium ceric nitrate is added for reaction for 8h, and the product is filtered, washed by methanol, washed by deionized water and dried to obtain the graft copolymerization nano-cellulose. Putting the materials into 1mol/L hydroxylamine solution according to the bath ratio of 1:45, reacting for 6h at 70 ℃, and sequentially washing products with methanol, deionized water and drying to prepare the bisamidoxime nano-cellulose material;
adding 40mL of 0.01mol/L silver nitrate solution into 30mL of 1 wt% bisamidoxime microcrystalline cellulose dispersion, and treating for 45min in a 600W ultrasonic cell crusher; after washing and centrifuging the diamidoxime microcrystalline cellulose, re-dispersing the diamidoxime microcrystalline cellulose in 25mL of deionized water; adding 20mL of 4 wt% dialdehyde chitosan solution into the reaction system, and reacting for 5h at 80 ℃ to obtain the silver-loaded bisamidoxime microcrystalline cellulose/chitosan composite sol.
Adding 15mL of 10 wt% silk fibroin solution into the silver-loaded diamidoxime microcrystalline cellulose/chitosan composite sol, and uniformly stirring to form blended sol. And (3) ultrasonically defoaming the blended sol, injecting the blended sol into a mold, freezing the mixture at the temperature of-50 ℃ for 8 hours, and drying the mixture to obtain the silver-loaded diamidoxime microcrystalline cellulose/chitosan/fibroin composite aerogel.
The dialdehyde chitosan solution, the diamidooxime cellulose and the fibroin solution used in this example were prepared according to methods 1, 2 and 3, respectively, described above.
Taking the silver-loaded diamidoxime microcrystalline cellulose/chitosan/fibroin composite aerogel prepared in the above example 1 as an example, further research and analysis are carried out. FIG. 1 shows the scanning electron microscope image of the microcrystalline cellulose carrying silver diamine oxime. As can be seen, the loading of the particulate matter was observed on the surface of the bisaminooxime microcrystalline cellulose. After further amplification, as shown in fig. 2, it can be clearly seen that the nano silver is uniformly distributed and in a single-layer dispersion state, and the particle size distribution is concentrated and is about 20 nm. The good distribution and dispersion state benefits from the strong coordination between abundant functional groups on the surface of the diamidoxime microcrystalline cellulose and metal ions. In addition, the material design has the advantages that: firstly, the diamidoxime microcrystalline cellulose provides a good carrier effect for the distribution of nano silver particles, and the agglomeration phenomenon caused by the preparation of aerogel by directly blending nano particles is avoided; secondly, the bisamidoxime microcrystalline cellulose improves the fixation of the nano silver particles in the aerogel and prevents the nano silver particles from running off in the use of a fluid system.
Fig. 3 is a scanning electron microscope image of the silver-loaded bisamidoxime microcrystalline cellulose/chitosan/fibroin composite aerogel, and it can be seen from the image that the composite aerogel is in a lamellar porous structure, and the interlayer distance is 50-150 μm. Silver-carrying bisamidoxime microcrystalline cellulose with a rod-shaped structure can be obviously found among pores. On further enlargement, the rod-like material surface will be as shown in fig. 1 and 2.
Fig. 4 and 5 are diagrams of the bacteriostatic effect of the fibroin/chitosan composite aerogel and the silver-loaded diammine oxime cellulose/chitosan/fibroin composite aerogel respectively. Fig. 4 is a diagram showing the bacteriostatic effect of the fibroin/chitosan composite aerogel on staphylococcus aureus, and in order to facilitate the operation of bacteriostatic experiments, the composite aerogel is compressed into a sheet shape before testing. As can be seen from the figure, no bacteriostatic zone is observed around the fibroin/chitosan composite aerogel, which indicates that the aerogel has no effective bacteriostatic action on escherichia coli. While the occurrence of zones of inhibition was clearly observed for both aerogels in fig. 5. Comparison shows that the addition amount of the silver-loaded diammine oxime microcrystalline cellulose plays a crucial role in inhibiting the bacteria of the aerogel, and the size of the inhibition zone is increased along with the increase of the addition amount of the silver-loaded diammine oxime cellulose, for example, the size of the inhibition zone in fig. 5(b) is obviously larger than that in fig. 5 (a). The appearance of the bacteriostatic zone verifies the bacteriostatic action of the aerogel and provides a theoretical basis for the application of the aerogel in the fields of tissue engineering, medical dressings and the like.
The foregoing has described the general principles, principal features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (5)
1. The preparation method of the silver-loaded diamidoxime cellulose/chitosan/fibroin composite aerogel is characterized in that the aerogel comprises the following components in parts by weight, 1-5 parts of diamidoxime cellulose, 0.05-2 parts of nano silver, 3-7 parts of fibroin and 3-7 parts of dialdehyde chitosan, and the preparation method comprises the following steps:
preparation of S1 silver-carrying bisamidoxime cellulose/chitosan
Adding 0.001-0.1 mol/L silver nitrate solution into 1.5-10 wt% of amidoxime-hydroxylamine oxime cellulose dispersion according to the volume ratio of 1: 10-100: 1, and treating in an ultrasonic cell crusher with the power set at 500-1200W for 15-90 min; taking out the product, washing, centrifuging, and uniformly dispersing in fresh deionized water again, wherein the deionized water is 0.5-2 times of the diamidoxime cellulose dispersion liquid in volume; then adding 0.5-5 wt% of dialdehyde chitosan solution into a reaction system, and reacting for 0.5-6 h at 50-90 ℃ to obtain silver-loaded bisamidoxime cellulose/chitosan composite sol;
formation of S2 blend Sol
Adding a fibroin solution with the concentration of 4-15 wt% into the silver-loaded diamidoxime cellulose/chitosan composite sol according to the volume ratio of 1: 1-1: 100, and uniformly stirring to form silver-loaded diamidoxime cellulose/chitosan/fibroin blended sol;
preparation of S3 composite aerogel
Ultrasonically defoaming the blended sol, injecting the blended sol into a mold, freezing the mixture at-50 ℃ for 4-10 hours, and drying the mixture to obtain silver-loaded diamineoxime cellulose/chitosan/fibroin composite aerogel;
wherein the preparation step of the diamidoxime cellulose in the step S1 is as follows:
step 1, placing cellulose into a NaOH solution with the concentration of 0.5-5 wt% according to the bath ratio of 1: 100-1: 10, and boiling for 30-150 min; then, placing the mixture in 10-30 wt% NaOH solution according to the bath ratio of 1: 100-1: 10, and stirring for 30-180 min at room temperature; filtering, washing and drying to obtain the alkalized cellulose;
step 2, placing the alkalized cellulose into acetone according to a bath ratio of 1: 20-1: 50, and condensing and refluxing for 10-45 min under the protection of nitrogen at 50-60 ℃; then adding 2-cyano-3-ethoxy ethyl acrylate, wherein the weight of the 2-cyano-3-ethoxy ethyl acrylate is 0.2-2 times that of the alkalized cellulose, magnetically stirring for 10-45 min, then adding ammonium ceric nitrate, and continuing to react for 1-8 h, wherein the ammonium ceric nitrate is 0.2-3% of the alkalized cellulose by mass; filtering the product, washing with methanol and water for several times, and drying to obtain the graft copolymer cellulose;
and 3, adding the graft copolymerization cellulose into 1mol/L hydroxylamine solution according to a bath ratio of 1: 15-1: 50, reacting for 1-6 h under the conditions of 65-75 ℃ and magnetic stirring, and sequentially carrying out methanol washing and drying on the product to obtain the diaminooxime cellulose.
2. The method for preparing silver-loaded diamidoxime cellulose/chitosan/fibroin composite aerogel according to claim 1, wherein the preparation process of the dialdehyde chitosan in the step S1 comprises the following steps: adding chitosan into an acetic acid solution with the concentration of 2 wt% according to the bath ratio of 1: 100-1: 10, and stirring until the chitosan is completely dissolved to obtain a chitosan solution; introducing nitrogen, adding a sodium periodate solution into a chitosan solution, wherein the sodium periodate is 13-66% of the chitosan by mass, oxidizing the chitosan solution at 30-60 ℃ in the dark for 1-10 h, adding ethylene glycol to stop the reaction, freeze-drying to obtain dialdehyde chitosan, and dissolving the dialdehyde chitosan in deionized water to prepare dialdehyde chitosan solutions with different concentrations.
3. The preparation method of the silver-loaded diamidoxime cellulose/chitosan/fibroin composite aerogel according to claim 2, wherein the deacetylation degree of chitosan is 85-95%.
4. The preparation method of the silver-loaded diamidoxime cellulose/chitosan/fibroin composite aerogel according to claim 3, wherein the fibroin solution in the step S2 is prepared by the following steps: putting raw silk into 0.3-3 wt% of Na according to a bath ratio of 1: 20-1: 1002CO3Treating the solution at 95-100 ℃ for 30min, circulating for three times, taking out the silk fibroin fibers, cleaning, drying, and placing the silk fibroin fibers in CaCl with the molar ratio of 1:8:2 according to the bath ratio of 1: 10-1: 502/H2O/C2H5And (2) in the OH mixed solution, magnetically stirring for 2-6 h at 78-88 ℃, centrifuging to remove undissolved silk fibroin fibers to obtain a light yellow silk fibroin solution, dialyzing for 24-72 h, and concentrating polyethylene glycol to obtain the silk fibroin solution.
5. The preparation method of the silver-loaded bisamidoxime cellulose/chitosan/fibroin composite aerogel according to claim 4, wherein the cellulose is one or a mixture of rod-shaped microcrystalline cellulose and/or nanocellulose.
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