CN115944772A - Bacterial cellulose-polydopamine-MXene @ AgNPs antibacterial hemostatic sponge and preparation method and application thereof - Google Patents
Bacterial cellulose-polydopamine-MXene @ AgNPs antibacterial hemostatic sponge and preparation method and application thereof Download PDFInfo
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- CN115944772A CN115944772A CN202310090251.2A CN202310090251A CN115944772A CN 115944772 A CN115944772 A CN 115944772A CN 202310090251 A CN202310090251 A CN 202310090251A CN 115944772 A CN115944772 A CN 115944772A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
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Abstract
The invention belongs to the technical field of biomedicine, and particularly relates to a bacterial cellulose-polydopamine-MXene @ AgNPs antibacterial hemostatic sponge as well as a preparation method and application thereof. The preparation method provided by the invention comprises the following steps: mixing water-soluble silver salt and single-layer MXene nanosheet water dispersion to obtain MXene @ AgNPs composite nanomaterial; and mixing the MXene @ AgNPs composite nano material with the bacterial cellulose gel modified by polydopamine crosslinking to obtain the bacterial cellulose-polydopamine-MXene @ AgNPs composite gel. The bacterial cellulose-polydopamine-MXene @ AgNPs composite gel and the antibacterial hemostatic sponge prepared by the preparation method provided by the invention have good mechanical properties and biocompatibility, have good antibacterial effect on escherichia coli and staphylococcus aureus under the assistance of near infrared light, and can be applied to skin wound healing under the condition of bacterial infection.
Description
Technical Field
The invention belongs to the technical field of biomedicine, and particularly relates to a bacterial cellulose-polydopamine-MXene @ AgNPs antibacterial hemostatic sponge as well as a preparation method and application thereof.
Background
The skin is the largest organ of the human body, can prevent various nutrient substances and water in the organism from losing while covering the whole body, and can also serve as a physical barrier for preventing microorganisms or harmful substances from invading the organism. When the skin is damaged by physical trauma or chemical erosion, the ability of the skin to protect the body is impaired, microorganisms in the environment can easily invade the body from the wound and multiply, and the wound is in a severe infection state when the bacteria removing ability of the body is not enough to limit the bacterial reproduction. After bacterial infection, the inflammatory response and local tissue necrosis may prevent wound healing, and in severe cases, may lead to bacteremia or immune dysfunction. Therefore, wound dressings that promote wound healing and inhibit bacterial growth are critical for skin lesion repair.
At present, most of the matrix materials of the common synthetic hydrogel wound dressing are prepared from one or more materials of polysaccharides, polypeptides, alcohol or acrylic acid and derivatives thereof, so that the mechanical strength is poor, the antibacterial activity is poor, and the requirements of patients on skin wound healing under the condition of bacterial infection factors are difficult to meet.
Disclosure of Invention
The invention aims to provide a bacterial cellulose-polydopamine-MXene @ AgNPs antibacterial hemostatic sponge and a preparation method and application thereof.
In order to achieve the above purpose, the invention provides the following technical scheme:
the invention provides a preparation method of bacterial cellulose-polydopamine-MXene @ AgNPs composite gel, which comprises the following steps:
mixing water-soluble silver salt and the single-layer MXene nanosheet water dispersion, carrying out reduction reaction, and loading silver nanoparticles on the surface of the single-layer MXene nanosheet to obtain an MXene @ AgNPs composite nanomaterial;
and mixing the MXene @ AgNPs composite nano material with the bacterial cellulose gel modified by polydopamine crosslinking to perform crosslinking reaction to obtain the bacterial cellulose-polydopamine-MXene @ AgNPs composite gel.
Preferably, the MXene @ AgNPs composite nano material and the polydopamine crosslinking modified bacterial cellulose gel are mixed to obtain a gel mixture, and the MXene @ AgNPs composite nano material in the gel mixture accounts for 0.02-0.2% of the mass percentage.
Preferably, the temperature of the crosslinking reaction is 50-70 ℃, and the time of the crosslinking reaction is 1-10 h.
Preferably, the preparation method of the polydopamine crosslinking modified bacterial cellulose gel comprises the following steps:
mixing a dopamine hydrochloride solution with the bacterial cellulose gel, and heating for a crosslinking reaction to obtain the polydopamine crosslinking modified bacterial cellulose gel; the temperature of the crosslinking reaction is 50-70 ℃.
Preferably, the mass percentage content of the bacterial cellulose in the bacterial cellulose gel is 0.5-5%; the ratio of the volume of the bacterial cellulose gel to the mass of the dopamine hydrochloride is 5mL (1-5) mg.
Preferably, the mass ratio of the water-soluble silver salt to the MXene nanosheets is 1; the temperature of the reduction reaction is room temperature, the time of the reduction reaction is 1-10 h, the reduction reaction is carried out under the condition of stirring, and the rotating speed of the stirring is 400-600 rpm.
The invention provides bacterial cellulose-polydopamine-MXene @ AgNPs composite gel prepared by the preparation method in the technical scheme, which comprises polydopamine crosslinking modified bacterial cellulose gel and MXene @ AgNPs composite nano-material loaded on the bacterial cellulose gel through crosslinking reaction with polydopamine.
The invention provides a preparation method of bacterial cellulose-polydopamine-MXene @ AgNPs antibacterial hemostatic sponge, which comprises the following steps:
and (2) freeze-drying the bacterial cellulose-polydopamine-MXene @ AgNPs composite gel to obtain the bacterial cellulose-polydopamine-MXene @ AgNPs antibacterial hemostatic sponge.
The invention provides the bacterial cellulose-polydopamine-MXene @ AgNPs antibacterial hemostatic sponge prepared by the preparation method in the technical scheme, which comprises polydopamine crosslinking modified bacterial cellulose and MXene @ AgNPs composite nano-material loaded on the bacterial cellulose through crosslinking reaction with polydopamine;
the bacterial cellulose-polydopamine-MXene @ AgNPs antibacterial hemostatic sponge has a three-dimensional porous loose structure.
The invention provides application of the bacterial cellulose-polydopamine-MXene @ AgNPs composite gel or the bacterial cellulose-polydopamine-MXene @ AgNPs antibacterial hemostatic sponge in preparation of skin wound dressings.
The invention provides a preparation method of bacterial cellulose-polydopamine-MXene @ AgNPs composite gel, which comprises the following steps: mixing a water-soluble silver salt and the single-layer MXene nanosheet water dispersion, carrying out reduction reaction, and loading silver nanoparticles on the surface of the single-layer MXene nanosheet to obtain an MXene @ AgNPs composite nanomaterial; and mixing the MXene @ AgNPs composite nano material with the bacterial cellulose gel modified by polydopamine crosslinking to perform crosslinking reaction to obtain the bacterial cellulose-polydopamine-MXene @ AgNPs composite gel. According to the preparation method provided by the invention, on one hand, the Bacterial Cellulose (BC) gel is used as the matrix of the composite material, the BC gel has a nano-network structure, a high specific surface area and high water absorption capacity, and the composite gel has good gas and liquid permeability while the mechanical strength of the composite gel material is improved; on the other hand, the composite nanometer material is prepared by chemically modifying a BC gel matrix material by using a large number of active amino groups on PDA through using Polydopamine (PDA) as a medium and then crosslinking MXene @ AgNPs, so that the use of polydopamine is beneficial to the effective loading of the MXene-AgNPs nanometer composite on BC and can enhance the elastic deformation capacity of BC; on the other hand, the MXene nanosheets and the silver nanoparticles have a synergistic antibacterial effect, and with the assistance of near infrared light of 808 nanometers, the MXene nanosheets can play an excellent photothermal conversion treatment effect (PTT) by virtue of an LSPR effect, the permeability of bacterial cell membranes is improved by heat energy induced by the PTT, and on the other hand, can also quickly conduct electrons to activate AgNPs to generate Ag + And ROS, thereby causing damage to the bacteria, thereby achieving the desired synergistic antimicrobial profile.
Meanwhile, the preparation method provided by the invention adopts a one-pot two-step method, the preparation method is simple, the cost is low, the storage and the transportation are easy, the raw materials are green and pollution-free from the preparation process, and the enterprise production is facilitated.
Further, in the invention, the preparation method of the polydopamine cross-linked modified bacterial cellulose gel comprises the following steps: mixing dopamine hydrochloride and bacterial cellulose gel, heating for cross-linking reaction to obtain polydopamine cross-linked modified bacterial cellulose gel; the temperature of the crosslinking reaction is 50-70 ℃. According to the invention, the cross-linking reaction of dopamine and bacterial cellulose is carried out at 50-70 ℃, so that the oxidative polymerization of dopamine is facilitated, the dopamine is more fully combined on the bacterial cellulose reticular structure, and the agglomeration phenomenon caused by too fast self-polymerization of dopamine when a catalyst is used can be avoided.
The invention provides bacterial cellulose-polydopamine-MXene @ AgNPs composite gel prepared by the preparation method in the technical scheme, which comprises polydopamine crosslinking modified bacterial cellulose gel and MXene @ AgNPs composite nano-material loaded on the bacterial cellulose gel through crosslinking reaction with polydopamine. The bacterial cellulose-polydopamine-MXene @ AgNPs composite gel provided by the invention has good mechanical properties and biocompatibility, has good antibacterial effect on escherichia coli and staphylococcus aureus under the assistance of near infrared light, and can be applied to skin wound healing under the condition of bacterial infection.
The invention provides the bacterial cellulose-polydopamine-MXene @ AgNPs antibacterial hemostatic sponge prepared by the preparation method in the technical scheme, which comprises polydopamine crosslinking modified bacterial cellulose and MXene @ AgNPs composite nano-material loaded on the bacterial cellulose through crosslinking reaction with polydopamine; the bacterial cellulose-polydopamine-MXene @ AgNPs antibacterial hemostatic sponge has a three-dimensional porous loose structure. The interior of the bacterial cellulose-polydopamine-MXene @ AgNPs antibacterial hemostatic sponge is of a three-dimensional porous loose structure, so that the wound blood and leachate can be quickly absorbed, and the framework support structure of the bacterial cellulose provides effective mechanical strength; the poly-dopamine is beneficial to the effective load of MXene-AgNPs nano composite and the enhancement of the elastic deformation capability of bacterial cellulose; the MXene-AgNPs composite nano material has good antibacterial effect on escherichia coli and staphylococcus aureus under the assistance of near infrared light, and can be applied to skin wound healing under the condition of bacterial infection factors.
Drawings
FIG. 1 is an exemplary flowchart of a method for preparing bacterial cellulose-polydopamine-MXene @ AgNPs antibacterial hemostatic sponge according to an embodiment of the present invention;
fig. 2-1 is an optical physical diagram and SEM image of the Bacterial Cellulose (BC) sponge prepared in comparative example 1, the polydopamine cross-linking modified Bacterial Cellulose (BCP) sponge prepared in comparative example 2, the bacterial cellulose-polydopamine-MXene (BCPM) sponge prepared in comparative example 3, and the bacterial cellulose-polydopamine-MXene @agnps (BCPMAg) sponge prepared in example 1 according to the present invention;
FIG. 2-2 is SEM images of Bacterial Cellulose (BC) sponge prepared in comparative example 1, polydopamine cross-linked modified Bacterial Cellulose (BCP) sponge prepared in comparative example 2, bacterial cellulose-polydopamine-MXene (BCPM) sponge prepared in comparative example 3, and bacterial cellulose-polydopamine-MXene @ AgNPs (BCPMAg) sponge prepared in example 1 according to the present invention;
FIG. 3-1 is a TEM representation of the product MXene, MXene-AgNPs prepared in example 1 of the present invention;
FIG. 3-2 is a mapping characterization chart of the product of MXene-AgNPs prepared in example 1 of the present invention;
FIGS. 3 to 3 are graphs showing the analysis of the element content of MXene-AgNPs prepared in example 1 of the present invention;
FIG. 4 is the porosity of the four sponges BC, BCP, BCPM, and BCPMAg prepared according to examples of the present invention and comparative examples;
FIG. 5 is a graph showing the hemostasis of the BC, BCP, BCPM, and BCPMAg sponges prepared according to the examples of the present invention and comparative examples;
FIG. 6 is a graph showing the growth of the four sponges, BC, BCP, BCPM, and BCPMAg, prepared according to the examples and comparative examples of the present invention, on agar plates after incubation with E.coli and Staphylococcus aureus;
FIG. 7 shows the bactericidal activity of the BC, BCP, BCPM, and BCPMAg sponges prepared according to the examples of the present invention and comparative examples.
Detailed Description
The invention provides a preparation method of bacterial cellulose-polydopamine-MXene @ AgNPs composite gel, which comprises the following steps:
mixing a water-soluble silver salt and the single-layer MXene nanosheet water dispersion, carrying out reduction reaction, and loading silver nanoparticles on the surface of the single-layer MXene nanosheet to obtain an MXene @ AgNPs composite nanomaterial;
and mixing the MXene @ AgNPs composite nano material with the bacterial cellulose gel modified by polydopamine crosslinking to perform crosslinking reaction to obtain the bacterial cellulose-polydopamine-MXene @ AgNPs composite gel.
In the present invention, all the preparation starting materials/components are commercially available products well known to those skilled in the art unless otherwise specified.
According to the invention, a water-soluble silver salt and a single-layer MXene nanosheet water dispersion are mixed (hereinafter referred to as first mixing) to generate a reduction reaction, and silver nanoparticles are loaded on the surface of the single-layer MXene nanosheet to obtain the MXene @ AgNPs composite nanomaterial.
In the present invention, the water-soluble silver salt is particularly preferably silver nitrate.
In the present invention, the water-soluble silver salt is preferably used in the form of an aqueous solution of a water-soluble silver salt at the time of the first mixing. The aqueous solution of the water-soluble silver salt is preferably ready for use.
In the present invention, the mass concentration of the aqueous solution of the water-soluble silver salt is preferably 0.5 to 5.0mg/mL, and more preferably 0.8 to 4.5mg/mL.
In the present invention, the monolayer MXene is preferably a two-dimensional transition metal carbide, nitride or boride. The chemical general formula of the single-layer MXene is shown as formula 1: m is a group of n+1 X n T x Formula 1; n in formula 1 is 1-3, M in formula 1 is an early transition metal element, and particularly preferably Mo, V, ti, zr or Nb; x in formula 1 is boron, carbon or nitrogen element, T in formula 1 x Refers to active functional groups such as-F, -OH, = O and the like bonded on the surface of two-dimensional transition metal carbide, nitride or boride.
In the present invention, the monolayer MXene is particularly preferably a monolayer Ti 3 C 2 T X 。
The present invention preferably prepares the monolayer MXene by chemical liquid phase etching of the MAX phase material. In the present invention, the MAX phase material is particularly preferably Ti 3 AlC 2 。
In the invention, the preparation method of the single-layer MXene nanosheet aqueous dispersion preferably comprises the following steps:
mixing the MAX phase material and an etching solution, carrying out chemical etching, and then carrying out first solid-liquid separation to obtain an MXene material with a multilayer structure;
and dispersing the MXene material with the multilayer structure in water, performing second solid-liquid separation after ultrasonic crushing, and taking filtrate to obtain a monolayer MXene nanosheet aqueous dispersion.
The method comprises the steps of mixing MAX phase materials and etching solution, carrying out first solid-liquid separation after chemical etching, and taking solid products to obtain MXene materials with multilayer structures. In the present invention, the etching solution is preferably a mixed solution of LiF and HCl. In the present invention, the method for preparing the mixed solution of LiF and HCl preferably includes the steps of: dissolving LiF in water to obtain a LiF solution; and mixing the LiF solution and the HCl solution to obtain a mixed solution of LiF and HCl. In the present invention, the molar ratio of the mass of LiF to the HCl is preferably (1 to 3) g (0.1 to 0.3) mol. In the present invention, the water is preferably ultrapure water, and the ratio of the mass of the LiF to the volume of the water is preferably (1 to 3) g (5 to 10) mL. The molar concentration of the HCl solution is preferably 5-10 mol/L, and the volume ratio of the HCl solution to the water is preferably (10-30) to (5-10). In the invention, the temperature of the chemical etching is preferably 35 ℃, the heat preservation time of the chemical etching is preferably 12-36 h, the chemical etching is preferably carried out under the condition of stirring, the rotating speed of the stirring is preferably 400-600 rpm, and the chemical etching is preferably carried out under the condition of constant-temperature water bath. The invention adopts a chemical liquid phase etching method to preferentially select a LiF and HCl mixed solution as an etching solution, aluminum layer atoms in MAX phase materials are selectively etched, and positive ions Li + Insertion of M in the reaction n+1 X n Between layers, the interlayer spacing is enlarged and the interlayer force is weakened to be easily peeled off into a two-dimensional state. In the invention, the first solid-liquid separation is preferably centrifugal separation, the temperature of the centrifugal separation is preferably 4 ℃, and the rotating speed of the centrifugal separation is preferably 4000-6000 rpm. The present invention preferably proceeds fromThe excess etching solution is removed by the first solid-liquid separation.
In the invention, the first solid-liquid separation is carried out to obtain a solid-phase product, and the solid-phase product is preferably subjected to post-treatment to obtain the MXene material with a multilayer structure. In the present invention, the post-treatment preferably comprises the steps of: carrying out third solid-liquid separation after the solid-phase product and HCl are subjected to heavy suspension precipitation to obtain a first solid-phase product; and alternately centrifuging and washing the first solid-phase product by adopting ultrapure water and absolute ethyl alcohol until the pH value of the supernatant is more than or equal to 5, and obtaining the MXene material with the multilayer structure as the solid product. The preferred removal of AlCl by HCl resuspension of the pellet in accordance with the invention 3 And the like by-products of the reaction.
After obtaining the MXene material with the multilayer structure, dispersing the MXene material with the multilayer structure in water, carrying out ultrasonic crushing, carrying out second solid-liquid separation, and taking filtrate to obtain a single-layer MXene nanosheet water dispersion. The MXene material of the multilayer structure is preferably transferred to a brown bottle and then dispersed with water, particularly preferably milli-Q water. In the present invention, the ultrasonication is preferably carried out in a protective gas atmosphere, and the protective gas is preferably nitrogen. The ultrasonic disruption is preferably carried out under the ice-water bath condition, the time of the ultrasonic disruption is preferably 1 to 5 hours, and the power of the ultrasonic disruption is preferably 100 to 500W. The MXene obtained by the method is preferably crushed into colloidal solution with uniform size by adopting a low-temperature liquid-phase ultrasonic method. In the invention, the second solid-liquid separation is preferably centrifugal separation, the temperature of the centrifugal separation is preferably 4 ℃, the rotation speed of the centrifugal separation is preferably 4000-6000 rpm, the time of the centrifugal separation is preferably 30-90 min, and after the centrifugal separation, a supernatant is taken to obtain the MXene nanosheet aqueous dispersion.
In the invention, the single-layer MXene nanosheet aqueous dispersion is preferably transferred to a Sichuan cattle bottle and stored under nitrogen.
In the present invention, the mass ratio of the water-soluble silver salt to the monolayer MXene nanoplatelet is preferably 1.
In the present invention, the temperature of the reduction reaction is preferably room temperature, the time of the reduction reaction is preferably 1 to 10 hours, more preferably 2 to 8 hours, the reduction reaction is preferably performed under stirring, and the rotation speed of the stirring is preferably 400 to 600rpm, more preferably 450 to 550rpm.
After obtaining the MXene @ AgNPs composite nano material, the MXene @ AgNPs composite nano material is mixed with the bacterial cellulose gel modified by polydopamine crosslinking (hereinafter referred to as second mixing), and crosslinking reaction is carried out to obtain the bacterial cellulose-polydopamine-MXene @ AgNPs composite gel.
In the invention, the preparation method of the polydopamine cross-linked modified bacterial cellulose gel preferably comprises the following steps:
mixing a dopamine hydrochloride solution with bacterial cellulose gel, and heating to perform a crosslinking reaction (hereinafter referred to as a first crosslinking reaction) to obtain the polydopamine crosslinking modified bacterial cellulose gel; the temperature of the first crosslinking reaction is 50-70 ℃.
In the present invention, the mass concentration of the dopamine hydrochloride solution is preferably 1 to 10mg/mL.
In the invention, the dopamine hydrochloride can be partially self-polymerized and also partially cross-linked with the bacterial cellulose, and the self-polymerized polydopamine can be adhered to the surface of the bacterial cellulose to form a polydopamine coating.
In the invention, the mass percentage content of the bacterial cellulose in the bacterial cellulose gel is preferably 0.5-5%, and more preferably 1-4.5%.
In the invention, the ratio of the volume of the bacterial cellulose gel to the mass of the dopamine hydrochloride is preferably 5mL (1-5) mg, and more preferably 5mL (1.5-4.5) mg.
In the present invention, the first crosslinking reaction is preferably carried out in a closed reaction vessel, and in the practice of the present invention, the closed reaction vessel is particularly preferably a brown sealed bottle. In the present invention, the temperature of the first crosslinking reaction is preferably 50 to 70 ℃, more preferably 55 to 65 ℃; the holding time for the first crosslinking reaction is preferably 6 to 24 hours, more preferably 10 to 20 hours. The first crosslinking reaction is preferably carried out under stirring conditions, and the first crosslinking reaction is preferably carried out under water bath conditions. In the invention, during the first crosslinking reaction, the dopamine and the bacterial cellulose are subjected to crosslinking reaction, and part of the dopamine is also subjected to self-crosslinking polymerization reaction, so that a gel solution formed by crosslinking polydopamine and the bacterial cellulose is finally formed, and the polydopamine crosslinking modified bacterial cellulose gel is obtained.
In the invention, the MXene @ AgNPs composite nano material and the polydopamine crosslinking modified bacterial cellulose gel are mixed to obtain a gel mixture, wherein the MXene @ AgNPs composite nano material is 0.02-0.2% in mass percentage in the gel mixture.
In the present invention, the second mixing is preferably performed under the condition of ultrasound, and the time of ultrasound is preferably 30min.
In the present invention, the temperature of the crosslinking reaction is preferably 50 to 70 ℃, and the time of the crosslinking reaction is preferably 1 to 10 hours, and more preferably 1.5 to 8 hours.
The invention provides bacterial cellulose-polydopamine-MXene @ AgNPs composite gel prepared by the preparation method in the technical scheme, which comprises polydopamine crosslinking modified bacterial cellulose gel and MXene @ AgNPs composite nano-material loaded on the bacterial cellulose gel through crosslinking reaction with polydopamine.
The invention provides a preparation method of bacterial cellulose-polydopamine-MXene @ AgNPs antibacterial hemostatic sponge, which comprises the following steps:
and (2) freeze-drying the bacterial cellulose-polydopamine-MXene @ AgNPs composite gel to obtain the bacterial cellulose-polydopamine-MXene @ AgNPs antibacterial hemostatic sponge.
In the present invention, before the freeze drying, the bacterial cellulose-polydopamine-MXene @ AgNPs composite gel is preferably subjected to a pretreatment, and in the present invention, the pretreatment preferably comprises the following steps: pouring the bacterial cellulose-polydopamine-MXene @ AgNPs composite gel into a mold, and sequentially standing, precooling and freezing at low temperature to obtain the frozen bacterial cellulose-polydopamine-MXene @ AgNPs composite gel; and (3) carrying out freeze drying on the frozen bacterial cellulose-polydopamine-MXene @ AgNPs composite gel. In the invention, the temperature of the standing precooling is preferably-4 ℃ to-20 ℃, and more preferably-4 ℃ to-15 ℃; the heat preservation time for standing and precooling is preferably 2-4 h. The standing precooling can enable the bacterial cellulose-polydopamine-MXene @ AgNPs composite gel to be better fitted with the mold. In the present invention, the temperature of the low-temperature freezing is preferably-40 ℃ to-90 ℃, more preferably-45 ℃ to-85 ℃; the time of low-temperature freezing is preferably more than or equal to 12 hours.
In the present invention, the time for the freeze-drying is preferably not less than 24 hours.
The invention provides the bacterial cellulose-polydopamine-MXene @ AgNPs antibacterial hemostatic sponge prepared by the preparation method in the technical scheme, which comprises polydopamine crosslinking modified bacterial cellulose and MXene @ AgNPs composite nano-material loaded on the bacterial cellulose through crosslinking reaction with polydopamine;
the bacterial cellulose-polydopamine-MXene @ AgNPs antibacterial hemostatic sponge has a three-dimensional porous loose structure.
The invention provides application of the bacterial cellulose-polydopamine-MXene @ AgNPs composite gel or the bacterial cellulose-polydopamine-MXene @ AgNPs antibacterial hemostatic sponge in preparation of skin wound dressings.
In the present invention, the Bacterial Cellulose (BC) gels used in the examples and comparative examples were purchased from Guilin Zihong science and technology; dopamine hydrochloride was purchased from shanghai alatin biochemical science and technology, ltd.
Example 1
According to the exemplary flow chart of the preparation method of the bacterial cellulose-polydopamine-MXene @ AgNPs antibacterial hemostatic sponge shown in FIG. 1:
uniformly dispersing 3.0g LiF into 10mL of ultrapure water, adding 30mL of 10M HCl solution, and stirring for 30min to obtain an etching solution;
adding 3.0g of Ti 3 AlC 2 Slowly adding powder (MAX phase material) into the etching solution, etching at 35 deg.C under constant temperature and magnetic stirring for 36 hr with stirring speed of 600rpm,transferring the black solution obtained by etching into a centrifuge tube, centrifuging at 6000rpm at 4 ℃ to remove excessive etching solution, then resuspending the precipitate with 3.0mol/L HCl, repeating the centrifuging step, and washing off residual AlCl 3 Reaction by-products. And alternately centrifuging and washing the supernatant for several times by using ultrapure water and absolute ethyl alcohol until the pH value of the supernatant is more than or equal to 5. The resulting precipitate was transferred to a brown bottle, which was placed in an ice-water bath for 5h with low-temperature sonication at 100W, with the addition of Mili-Q water and with nitrogen as a shielding gas. After the ultrasonic treatment is finished, centrifuging the ultrasonic reaction solution at the rotating speed of 6000rpm at 4 ℃ for 90min, transferring the supernatant to a Shuniu bottle, and filling nitrogen for storage to obtain a monolayer MXene nanosheet dispersion liquid, wherein the mass concentration of the monolayer MXene nanosheet dispersion liquid is 1mg/mL;
adding 5mL of silver nitrate solution with the mass concentration of 1mg/mL into 5mL of single-layer MXene dispersion liquid (wherein the mass ratio of the silver nitrate to the single-layer MXene is 1;
and (3) sucking 5.0mLBC gel into a 30mL brown reagent bottle, adding a dopamine hydrochloride solution (the mass concentration of the dopamine hydrochloride solution is 1mg/mL, and 5.0mg of dopamine hydrochloride powder is contained) into the brown reagent bottle, placing the whole system into a constant-temperature water bath stirrer at 60 ℃ and stirring for 5.0h, wherein the dopamine is uniformly dispersed in the BC system and is slowly polymerized in a fiber network of the bacterial cellulose. After the reaction is finished, polydopamine crosslinking modified bacterial cellulose gel is obtained;
transferring the MXene @ AgNPs composite nano material solution into the polydopamine crosslinking modified bacterial cellulose gel, performing ultrasonic dispersion for 30min, and stirring at the constant temperature of 60 ℃ for 5.0h. After the reaction is finished, obtaining bacterial cellulose-polydopamine-MXene @ AgNPs composite gel;
transferring the bacterial cellulose-polydopamine-MXene @ AgNPs composite gel into a 12-hole plate, cooling to room temperature, pre-freezing for 4h at-20 ℃ and freezing for 12h at-80 ℃, and freeze-drying for 24h to obtain the bacterial cellulose-polydopamine-MXene @ AgNPs antibacterial hemostatic sponge, which is marked as BC-PDA-MXene @ AgNPs and is referred to as BCPMAg for short.
FIG. 3-1 is a TEM representation of the product MXene and MXene-AgNPs prepared in this example; FIG. 3-2 is a mapping characterization chart of the product of MXene-AgNPs prepared in this example; as can be easily found from the comparison of the TEM images of MXene and MXene-AgNPs in the graph of 3-1, the successfully loaded silver nanoparticles on the surface of the nanosheet, the prepared MXene nanosheet is in a single-layer flaky shape, and the size of the MXene nanosheet is about 250-450nm, which meets the expected preparation requirement. Element mapping is carried out on the MXene nanosheets after the silver nanoparticles are loaded (as shown in figure 3-2), and element content analysis is further carried out on the MXene nanosheets after the silver nanoparticles are loaded (as shown in figure 3-3 and table 1), so that the loading of the silver nanoparticles can be further proved. The existence of elements such as C, ti, O, ag and the like can also be clearly observed, the Ti and the C elements are uniformly distributed, and the distribution of the Ag element proves the regularity of 'bright spots' in the TEM image. The silver nano particles are round under the observation of a high power lens, the particle size is within the range of 20-30nm, the surface distance of the lattice fringes is 0.23nm, and the lattice fringes correspond to the (111) surface of the silver nano particles.
TABLE 1 mapping characterisation of the product of MXene-AgNPs prepared in example 1 elemental analysis Table
Example 2
According to the exemplary flow chart of the preparation method of the bacterial cellulose-polydopamine-MXene @ AgNPs antibacterial hemostatic sponge shown in FIG. 1:
uniformly dispersing 3.0g of LiF into 10mL of ultrapure water, adding 10mL of 5M HCl solution, and stirring for 30min to obtain an etching solution;
1.0g of Ti 3 AlC 2 Slowly adding powder (MAX phase material) into etching solution, and magnetically stirring at constant temperature of 35 deg.CEtching for 12h at a stirring speed of 400rpm, transferring the black solution obtained by etching into a centrifuge tube, centrifuging at 4000rpm at 4 ℃ to remove excessive etching solution, then resuspending the precipitate with 0.3mol/L HCl, repeating the centrifuging step, and removing residual AlCl 3 Reaction by-products. And (4) alternately centrifuging and washing with ultrapure water and absolute ethyl alcohol for several times until the pH value of the supernatant is more than or equal to 5. The resulting precipitate was transferred to a brown bottle, which was placed in an ice-water bath for 1h under low temperature sonication with Mili-Q water and nitrogen as a blanket gas, at a sonication power of 500W. After the ultrasonic treatment is finished, centrifuging the ultrasonic reaction solution at the rotating speed of 6000rpm at 4 ℃ for 30min, transferring the supernatant to a Shuniu bottle, and filling nitrogen for storage to obtain a monolayer MXene nanosheet dispersion liquid, wherein the mass concentration of the monolayer MXene nanosheet dispersion liquid is 5.0mg/mL;
adding 5mL of silver nitrate solution with the mass concentration of 5.0mg/mL into 5mL of single-layer MXene dispersion liquid (wherein the mass ratio of the silver nitrate to the single-layer MXene is 1;
sucking 5.0mL of BC gel into a 30mL brown reagent bottle, adding a dopamine hydrochloride solution (the mass concentration of the dopamine hydrochloride solution is 1mg/mL, and 5.0mg of dopamine hydrochloride powder is contained), placing the whole system in a constant-temperature water bath stirrer at 60 ℃ and stirring for 5.0h, wherein dopamine is uniformly dispersed in the BC system and slowly polymerized in a fiber network of bacterial cellulose. After the reaction is finished, polydopamine crosslinking modified bacterial cellulose gel is obtained;
transferring the MXene @ AgNPs composite nano material solution into the polydopamine crosslinking modified bacterial cellulose gel, performing ultrasonic dispersion for 30min, and stirring at the constant temperature of 60 ℃ for 8.0h. After the reaction is finished, obtaining bacterial cellulose-polydopamine-MXene @ AgNPs composite gel;
transferring the bacterial cellulose-polydopamine-MXene @ AgNPs composite gel into a 12-hole plate, cooling to room temperature, pre-freezing for 4h at-10 ℃ and freezing for 12h at-80 ℃, and freeze-drying for 24h to obtain the bacterial cellulose-polydopamine-MXene @ AgNPs antibacterial hemostatic sponge, which is marked as BC-PDA-MXene @ AgNPs and is referred to as BCPMAg for short.
Example 3
According to an exemplary flow chart of the preparation method of the bacterial cellulose-polydopamine-MXene @ AgNPs antibacterial hemostatic sponge shown in FIG. 1:
uniformly dispersing 2.0g LiF into 10mL of ultrapure water, adding 30mL of 10M HCl solution, and stirring for 30min to obtain an etching solution;
2.0g of Ti 3 AlC 2 Slowly adding powder (MAX phase material) into etching solution, etching at 35 deg.C under constant temperature magnetic stirring for 36 hr with stirring speed of 600rpm, transferring the black solution obtained by etching into a centrifuge tube, centrifuging at 4 deg.C and 5000rpm to remove excessive etching solution, then re-suspending the precipitate with 1.0mol/L HCl, and repeating the centrifuging step to remove residual AlCl 3 Reaction by-products. And alternately centrifuging and washing the supernatant for several times by using ultrapure water and absolute ethyl alcohol until the pH value of the supernatant is more than or equal to 5. The resulting precipitate was transferred to a brown bottle, which was placed in an ice-water bath for 4h with low-temperature sonication at 500W, with the addition of Mili-Q water and with nitrogen as a shielding gas. After the ultrasound is finished, centrifuging the ultrasound reaction solution at the rotating speed of 6000rpm at the temperature of 4 ℃ for 90min, transferring the supernatant to a Sichuan cattle bottle, and filling nitrogen for preservation to obtain a monolayer MXene nanosheet dispersion liquid, wherein the mass concentration of the monolayer MXene nanosheet dispersion liquid is 1.0mg/mL;
adding 5mL of silver nitrate solution with the mass concentration of 1.0mg/mL into 5mL of single-layer MXene dispersion liquid (wherein the mass ratio of the silver nitrate to the single-layer MXene is 1;
and (3) sucking 5.0mLBC gel into a 30mL brown reagent bottle, adding a dopamine hydrochloride solution (the mass concentration of the dopamine hydrochloride solution is 1mg/mL, and 5.0mg of dopamine hydrochloride powder is contained) into the brown reagent bottle, placing the whole system into a constant-temperature water bath stirrer at 60 ℃ and stirring for 5.0h, wherein the dopamine is uniformly dispersed in the BC system and is slowly polymerized in a fiber network of the bacterial cellulose. After the reaction is finished, polydopamine crosslinking modified bacterial cellulose gel is obtained;
transferring the MXene @ AgNPs composite nano material solution into the polydopamine crosslinking modified bacterial cellulose gel, ultrasonically dispersing for 30min, and stirring at the constant temperature of 60 ℃ for 5.0h. After the reaction is finished, obtaining bacterial cellulose-polydopamine-MXene @ AgNPs composite gel;
transferring the bacterial cellulose-polydopamine-MXene @ AgNPs composite gel into a 12-hole plate, cooling to room temperature, pre-freezing for 3h at-4 ℃ and freezing overnight at-80 ℃, and freeze-drying for 24h to obtain the bacterial cellulose-polydopamine-MXene @ AgNPs antibacterial hemostatic sponge, which is marked as BC-PDA-MXene @ AgNPs and is referred to as BCPMAg for short.
Comparative example 1
And (3) sucking 5.0mLBC gel into a 30mL brown reagent bottle, placing the reagent bottle in a constant-temperature water bath stirrer at the temperature of 60 ℃ for stirring for 2 hours, transferring the BC gel into a 12-pore plate after stirring, pre-freezing the BC gel at the temperature of minus 20 ℃ after cooling to the room temperature, freezing the BC gel at the temperature of minus 80 ℃ overnight, and carrying out freeze drying for 24 hours to obtain the BC sponge.
Comparative example 2
And (3) sucking 5.0mLBC gel into a 30mL brown reagent bottle, adding a dopamine hydrochloride solution (the mass concentration of the dopamine hydrochloride solution is 1mg/mL, and 5.0mg of dopamine hydrochloride powder is contained) into the brown reagent bottle, placing the whole system into a constant-temperature water bath stirrer at 60 ℃ and stirring for 5.0h, wherein the dopamine is uniformly dispersed in the BC system and is slowly polymerized in a fiber network of the bacterial cellulose. And after the reaction is finished, obtaining polydopamine crosslinking modified bacterial cellulose gel, transferring the polydopamine crosslinking modified bacterial cellulose gel into a 12-hole plate, pre-freezing the polydopamine crosslinking modified bacterial cellulose gel at the temperature of-20 ℃ after cooling to the room temperature, freezing the polydopamine crosslinking modified bacterial cellulose gel overnight at the temperature of-80 ℃, and freeze-drying the polydopamine crosslinking modified bacterial cellulose gel for 24 hours to obtain BC/PDA sponge, namely BCP sponge.
Comparative example 3
Preparing a single-layer MXene nanosheet dispersion according to the method provided in example 1, wherein the mass concentration of the single-layer MXene nanosheet dispersion is 1mg/mL; and (2) sucking 5.0mLBC gel into a 30mL brown reagent bottle, adding a dopamine hydrochloride solution (the mass concentration of the dopamine hydrochloride solution is 1mg/mL, and the dopamine hydrochloride solution contains 5.0mg of dopamine hydrochloride powder), placing the whole system into a 60-DEG C constant-temperature water bath stirrer, stirring for 5.0h, uniformly dispersing the dopamine in a BC system, slowly polymerizing the dopamine in a bacterial cellulose fiber network, and obtaining the polydopamine crosslinking modified bacterial cellulose gel after the reaction is finished.
Transferring 5mL of Xene solution (1 mg/mL) into the reaction system, performing ultrasonic dispersion for 30min, and stirring at constant temperature of 60 ℃ for 0.5-5.0 h. After the reaction is finished, transferring the gel into a 12-pore plate, pre-freezing at the temperature of minus 20 ℃ after cooling to the room temperature, freezing overnight at the temperature of minus 80 ℃, and carrying out freeze drying for 24h to obtain BC/PDA-MXene sponge, which is referred to as BCPM sponge for short.
FIG. 2 is an optical physical diagram of the Bacterial Cellulose (BC) sponge prepared in comparative example 1, the polydopamine cross-linked modified Bacterial Cellulose (BCP) sponge prepared in comparative example 2, the bacterial cellulose-polydopamine-MXene (BCPM) sponge prepared in comparative example 3, and the bacterial cellulose-polydopamine-MXene @ AgNPs (BCPMAg) sponge prepared in example 1; the optical material diagram in fig. 2 shows that the BC sponge prepared in comparative example 1 of the present invention is pure white, the color of the BCP prepared in comparative example 2 is gradually oxidized to tan due to the polymerization of dopamine after the dopamine is cross-linked and compounded, the color of the whole BCPM sponge shows obvious dark green (the product of comparative example 3) after the MXene nanosheet is loaded, and the color of the whole BCPMAg sponge can also show brown yellow of silver nano besides green after the MXene-AgNPs nano compound is loaded.
As can be seen from the FE-SEM images of a series of sponges in FIG. 2, the sponges internally present a porous interconnected three-dimensional network structure.
Test example 1
In the test example, the porosities of the four sponges, namely BC, BCP, BCPM and BCPMAg, prepared in the examples and the comparative examples are tested, and the operation method of the experiment is as follows: a sample of sponge of the appropriate size (2.5 mm diameter and 0.5mm height) was selected, weighed accurately, recorded as M0, its diameter and thickness measured and the volume (v) calculated. Will be weighed in advanceThe heavy sample was soaked in absolute ethanol to saturation (ρ =0.7893 g/cm) 3 ) Then removed and weighed as M1. The porosity was calculated using the formula shown in equation 2:
porosity (%) = (M1-M0)/ρ v × 100% formula 2
FIG. 4 is a graph of the porosity of the four sponges BC, BCP, BCPM, and BCPMAg prepared according to examples of the invention and comparative examples; as can be seen from fig. 4, the aerogel porosity exhibited an increasing trend with the addition of dopamine and nanocomposite in the system. BC. The porosity of BC-PDA, BC-PDA-MXene-AgNPs was 38.962%, 55.559%, 60.022%, and 67.113%, respectively. The prepared composite sponge has a porous structure, is beneficial to absorbing tissue exudate, quickly absorbs blood at a wound to stop bleeding, and is suitable for the attached growth of new tissue cells.
Test example 2
In the test example, the blood coagulation performance of the four sponges BC, BCP, BCPM and BCPMAg prepared in the example and the comparative example is tested, and the operation method of the blood coagulation experiment is as follows:
determination of the blood coagulation index BCI with sheep blood or rat blood as sodium citrate anticoagulant: taking CaCl 2 After mixing 15. Mu.L (0.2M) of the solution with 150. Mu.L of anticoagulated blood sodium citrate, the solution was quickly dropped on a complex sponge (. About.10.0 mg). After incubation at 37 ℃ for 5 minutes, the sponge was immersed in deionized water to rupture the unsolidified red blood cells to obtain a hemoglobin solution. The absorbance of the hemoglobin solution at 542 nm was measured using a uv-vis spectrometer. The absorbance (Ac) of the control group (anticoagulated blood of the same dilution) was measured as a reference, and the absorbance of the sponge-treated blood was measured as Ae. The formula for calculating the blood coagulation index BCI is shown in formula 3:
BCI (%) = (Ae/Ac) × 100% formula 3
Fig. 5 shows the hemostatic conditions of the four sponges BC, BCP, BCPM and BCPMAg prepared in the examples and comparative examples of the present invention, and it can be shown from fig. 5 that the antibacterial sponge BPMA prepared by the present invention has good blood coagulation performance and can play a hemostatic role. Secondly, the hemolysis value is lower than 5%, and the biocompatibility is good.
Test example 3
In the test example, the antibacterial performance of the four sponges BC, BCP, BCPM and BCPMAg prepared in the example and the comparative example is researched, and the operation method of the antibacterial experiment is as follows:
and (3) amplification of strains: and (3) amplifying strains of Aureus and E.coli, putting a single colony of the strains streaked by a plate into 100mL broth culture medium, and shaking the strains at 180-250 rpm at 37 ℃ for 18-24 h.
Co-incubating the antibacterial material with bacterial liquid:
no near infrared light irradiation group: sterile 12-well plates were prepared. 200 mu L of the amplified bacterial liquid is taken and placed in a 5mL EP tube, 3.0mL of culture medium is added, the OD600 of the bacterial liquid is tested, and then the dilution ratio is gradually modified to obtain the diluted bacterial liquid with OD600 = 0.1. Diluting bacterial liquid to 10 times 6 After CFU, 5.0mL10 is taken 6 Mixing the CFU bacterial liquid with different antibacterial sponges, and placing the mixture in an incubator at 37 ℃ for 6 hours.
Near infrared light irradiation group: sterile 12-well plates were prepared. 200 mu L of the amplified bacterial liquid is taken and placed in a 5mL EP tube, 3.0mL of culture medium is added, the OD600 of the bacterial liquid is tested, and then the dilution ratio is gradually modified to obtain the diluted bacterial liquid with OD600 = 0.1. Diluting the bacterial liquid to 10 times 6 After CFU, 5.0mL of 10 was taken 6 Mixing the CFU bacterial liquid with different antibacterial sponges, irradiating for 10min at 808nm, and then placing in an incubator at 37 ℃ for growth for 6h.
Agar medium plate count: the co-incubation solution was diluted to 10 with medium 3 After shaking uniformly, draw 100. Mu.L of the diluted solution and spread on LB agar plate. Incubate overnight at 37 ℃ and take pictures to record the growth of the plates.
FIG. 6 shows the growth of the four sponges BC, BCP, BCPM and BCPMAg prepared in the examples and comparative examples of the present invention on an agar plate after incubation with Escherichia coli and Staphylococcus aureus, and it can be seen from FIG. 6 that the antibacterial sponges under the assistance of near infrared light have a more significant antibacterial effect compared to the experiment group without the assistance of near infrared light, and the upper surface of the plate of BCPMAg group is smooth and has no bacterial colony to survive, indicating that the sponges have antibacterial activity against both Staphylococcus aureus and Escherichia coli; from fig. 7, it can be seen that the bactericidal rates of the BCPMAg antibacterial sponge on staphylococcus aureus and escherichia coli under the assistance of near infrared light are respectively (99.9% and 99.9%).
Although the above embodiments have been described in detail, they are only a part of the embodiments of the present invention, not all of the embodiments, and other embodiments can be obtained without inventive step according to the embodiments, and all of the embodiments belong to the protection scope of the present invention.
Claims (10)
1. A preparation method of bacterial cellulose-polydopamine-MXene @ AgNPs composite gel is characterized by comprising the following steps:
mixing a water-soluble silver salt and the single-layer MXene nanosheet water dispersion, carrying out reduction reaction, and loading silver nanoparticles on the surface of the single-layer MXene nanosheet to obtain an MXene @ AgNPs composite nanomaterial;
and mixing the MXene @ AgNPs composite nano material with the bacterial cellulose gel modified by polydopamine crosslinking to perform crosslinking reaction to obtain the bacterial cellulose-polydopamine-MXene @ AgNPs composite gel.
2. The preparation method of claim 1, wherein the MXene @ AgNPs composite nanomaterial and the polydopamine crosslinking modified bacterial cellulose gel are mixed to obtain a gel mixture, and the mass percentage of the MXene @ AgNPs composite nanomaterial in the gel mixture is 0.02-0.2%.
3. The method according to claim 1 or 2, wherein the temperature of the crosslinking reaction is 50 to 70 ℃ and the time of the crosslinking reaction is 1 to 10 hours.
4. The preparation method of claim 1, wherein the preparation method of the polydopamine cross-linked modified bacterial cellulose gel comprises the following steps:
mixing a dopamine hydrochloride solution with bacterial cellulose gel, and heating to perform a crosslinking reaction to obtain the polydopamine crosslinking modified bacterial cellulose gel; the temperature of the crosslinking reaction is 50-70 ℃.
5. The preparation method according to claim 4, wherein the mass percentage of the bacterial cellulose in the bacterial cellulose gel is 0.5-5%; the ratio of the volume of the bacterial cellulose gel to the mass of the dopamine hydrochloride is 5mL (1-5) mg.
6. The preparation method according to claim 1, wherein the mass ratio of the water-soluble silver salt to the MXene nanosheets is 1; the temperature of the reduction reaction is room temperature, the time of the reduction reaction is 1-10 h, the reduction reaction is carried out under the condition of stirring, and the rotating speed of the stirring is 400-600 rpm.
7. The bacterial cellulose-polydopamine-MXene @ AgNPs composite gel prepared by the preparation method of any one of claims 1 to 6, characterized by comprising polydopamine cross-linking modified bacterial cellulose gel and MXene @ AgNPs composite nanomaterial loaded on the bacterial cellulose gel through cross-linking reaction with polydopamine.
8. A preparation method of bacterial cellulose-polydopamine-MXene @ AgNPs antibacterial hemostatic sponge is characterized by comprising the following steps:
freeze-drying the bacterial cellulose-polydopamine-MXene @ AgNPs composite gel of claim 7 to obtain the bacterial cellulose-polydopamine-MXene @ AgNPs antibacterial hemostatic sponge.
9. The bacterial cellulose-polydopamine-MXene @ AgNPs antibacterial hemostatic sponge prepared by the preparation method of claim 8, which is characterized by comprising polydopamine cross-linking modified bacterial cellulose and MXene @ AgNPs composite nano-material loaded on the bacterial cellulose through cross-linking reaction with polydopamine;
the bacterial cellulose-polydopamine-MXene @ AgNPs antibacterial hemostatic sponge has a three-dimensional porous loose structure.
10. The use of the bacterial cellulose-polydopamine-MXene @ AgNPs composite gel of claim 7 or the bacterial cellulose-polydopamine-MXene @ AgNPs antibacterial hemostatic sponge of claim 9 in the preparation of a skin wound dressing.
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| CN202310090251.2A CN115944772B (en) | 2023-01-13 | 2023-01-13 | Bacterial cellulose-polydopamine-MXene@AgNPs antibacterial hemostatic sponge and preparation method and application thereof |
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| CN108066814A (en) * | 2017-12-11 | 2018-05-25 | 常州市协旺纺织品有限公司 | A kind of preparation method of bacteria cellulose antiseptic dressing |
| CN109348694A (en) * | 2018-09-13 | 2019-02-15 | 上海大学 | High-strength flexible self-supporting electromagnetic wave shield film and preparation method thereof |
| CN111303449A (en) * | 2020-01-17 | 2020-06-19 | 华中科技大学 | Degradable electroactive bacterial cellulose/MXene composite hydrogel and preparation and application thereof |
| CN113980185A (en) * | 2021-12-13 | 2022-01-28 | 河南汇博医疗股份有限公司 | Amorphous silver-containing long-acting antibacterial hydrogel dressing with photo-crosslinking curing function and preparation method thereof |
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| CN108066814A (en) * | 2017-12-11 | 2018-05-25 | 常州市协旺纺织品有限公司 | A kind of preparation method of bacteria cellulose antiseptic dressing |
| CN109348694A (en) * | 2018-09-13 | 2019-02-15 | 上海大学 | High-strength flexible self-supporting electromagnetic wave shield film and preparation method thereof |
| CN111303449A (en) * | 2020-01-17 | 2020-06-19 | 华中科技大学 | Degradable electroactive bacterial cellulose/MXene composite hydrogel and preparation and application thereof |
| CN113980185A (en) * | 2021-12-13 | 2022-01-28 | 河南汇博医疗股份有限公司 | Amorphous silver-containing long-acting antibacterial hydrogel dressing with photo-crosslinking curing function and preparation method thereof |
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