CN114832831A - Composite nano enzyme synergistic catalytic fiber material and preparation method and application thereof - Google Patents
Composite nano enzyme synergistic catalytic fiber material and preparation method and application thereof Download PDFInfo
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- CN114832831A CN114832831A CN202210420339.1A CN202210420339A CN114832831A CN 114832831 A CN114832831 A CN 114832831A CN 202210420339 A CN202210420339 A CN 202210420339A CN 114832831 A CN114832831 A CN 114832831A
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- spinning
- nanoenzyme
- fiber material
- spinning solution
- glycolic acid
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- A61L2300/412—Tissue-regenerating or healing or proliferative agents
Abstract
The invention relates to a composite nano enzyme synergistic catalytic fiber material, a preparation method and application thereof, and belongs to the technical field of wound dressings. The composite nano enzyme synergistic catalysis fiber material is prepared by spinning a spinning solution A and a spinning solution B through electrostatic spinning and drying; the spinning solution A consists of polylactic acid-glycolic acid copolymer, manganese dioxide nanoenzyme, calcium peroxide and a spinning solvent, and the spinning solution B consists of polylactic acid-glycolic acid copolymer, ferroferric oxide nanoenzyme, calcium peroxide, benzoic acid and a spinning solvent. The composite nano enzyme synergistic catalytic fiber material can efficiently and continuously generate oxygen and hydroxyl free radicals at the same time, so that the catalytic fiber material has the effects of oxygen supply and antibiosis, remarkably promotes the healing of wounds, particularly the healing speed of chronic wounds of diabetes, is convenient to use, simple to prepare and store, and has the characteristic of absorbing seepage.
Description
Technical Field
The invention belongs to the technical field of wound dressings, and particularly relates to a composite nano-enzyme synergistic catalytic fiber material, a preparation method and an application thereof, in particular to an application of the composite nano-enzyme synergistic catalytic fiber material in preparation of a dressing for promoting wound healing, especially a dressing for diabetic chronic wound healing.
Background
Diabetics face the risk of chronic non-healing wounds, and even amputations, for their lifetime. Research shows that the main reason of chronic wounds of diabetes is the injury of new blood vessels caused by hypoxia at wounds. Under the condition of high-content glucose, the processes of hydroxylation, degradation, translation and the like of hypoxia inducible factors at chronic wounds are seriously interfered, so that the wounds of diabetics cannot deal with the ischemia condition of soft tissues by upwards regulating vascular endothelial growth factors, and further angiogenesis damage and slow wound healing are caused. In addition to endogenous causes, delayed healing of wounds is also associated with bacterial infections. Compared with the common people, the wounds of the diabetics contain higher content of sugar, the invasion of bacteria is more easily caused, and the local edema and anoxic environment of the wounds are favorable for the growth of the bacteria. Meanwhile, in the environment of high sugar content, the phagocytosis of the white blood cells of the diabetic patient is weakened, the killing capability is reduced, bacteria are not easy to be eliminated, and the infection area is further enlarged. For patients with lower immunity and resistance, it is more difficult for the wound to heal completely once it is infected with bacteria. Therefore, the difficulty of wound treatment for diabetic patients lies in effectively controlling the tissue infection caused by the neovascular injury and bacterial invasion caused by hypoxia at the wound.
In the prior art, the dressing for promoting the wound healing of a diabetic patient is mainly a hydrogel dressing, the principle of the dressing is that the wound healing is promoted by improving the antibacterial capacity of the wound, the problem of the injury of a new blood vessel caused by hypoxia at the wound cannot be solved, and the hydrogel has the defects of high storage condition, high clinical use difficulty and the like. For example, an antibacterial hydrogel dressing for repairing diabetic wound and its preparation method (publication No. CN113476645A) are disclosed, which is prepared by compounding TiO with a dressing 2 /Ag 3 PO 4 Phosphate suspension, polyacrylic acid (PAA) aqueous solution, calcium chloride aqueous solution and Glucose Oxidase (GO) x ) An aqueous solution; then mixing polyacrylic acid aqueous solution, calcium chloride aqueous solution and glucose oxidase aqueous solution, adding TiO under the condition of vigorous stirring 2 /Ag 3 PO 4 Phosphate suspension to obtain the antibacterial hydrogel dressing PAA @ TiO 2 /Ag 3 PO 4 @ GOx. The dressing can respond to phosphate radical in physiological environment to make Ca 2+ To induce gel degradation and release TiO 2 /Ag 3 PO 4 And GO x ，GO x Decompose glucose in wound surface, and reduce local blood sugar concentration. TiO 2 2 Catalysis of H under illumination 2 O 2 Generating active oxygen in cooperation with Ag + Sterilizing, further reducing the blood sugar concentration of the wound surface, maintaining long-acting effect, high antibacterial activity and low cytotoxicity, and promoting the healing of the diabetic wound.
Disclosure of Invention
The invention provides a composite nano enzyme synergistic catalytic fiber material, a preparation method and application thereof for solving the defects of the prior art, the composite nano enzyme synergistic catalytic fiber material can obviously improve the speed of wound healing, especially the healing speed of chronic wounds of diabetes, and has the characteristics of convenient use, simple preparation, simple storage and absorption of seepage.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows.
The composite nano enzyme synergistic catalysis fiber material is prepared by spinning a spinning solution A and a spinning solution B through electrostatic spinning and drying;
the spinning solution A consists of polylactic acid-glycolic acid copolymer (PLGA), an inner dopant and a spinning solvent, wherein the inner dopant A consists of manganese dioxide nanoenzyme and calcium peroxide in a mass ratio of 1 (1-9), the concentration of the polylactic acid-glycolic acid copolymer in the spinning solution A is 5-20 wt%, and the mass ratio of the inner dopant to the polylactic acid-glycolic acid copolymer is 1: 10;
the spinning solution B is composed of a polylactic acid-glycolic acid copolymer, an inner admixture B, benzoic acid and a spinning solvent, wherein the inner admixture B is composed of ferroferric oxide nanoenzyme and calcium peroxide in a mass ratio of 1 (1-9), the concentration of the polylactic acid-glycolic acid copolymer in the spinning solution B is 5-20 wt%, the concentration of the benzoic acid is 0.5-2 wt%, and the mass ratio of the inner admixture B to the polylactic acid-glycolic acid copolymer is 1: 10.
Preferably, the concentrations of the polylactic acid-glycolic acid copolymer in the spinning solution a and the spinning solution B are 10 wt%, respectively.
Preferably, the polylactic acid-glycolic acid copolymer has a molecular weight of 100000Da and a molar ratio of lactic acid to glycolic acid of 50: 50.
Preferably, the spinning solvent is hexafluoroisopropanol.
Preferably, in the spinning solution B, the mass ratio of the benzoic acid to the polylactic acid-glycolic acid copolymer is 1: 5.
Preferably, the calcium peroxide is prepared by the following method: fully mixing calcium chloride and polyvinylpyrrolidone in ethanol, carrying out ultrasonic treatment for 0.5-2h, adding ammonia water, continuously stirring for 0.5-2h, then adding hydrogen peroxide at the speed of 0.05-0.2mL/min, continuously stirring until light blue milky solution is obtained, washing with ethanol for multiple times, and drying at 60 ℃ to obtain monodisperse spheres, namely calcium peroxide;
the proportion of the calcium chloride, the polyvinylpyrrolidone, the ammonia water and the hydrogen peroxide is 0.1g to 0.35g to 1mL to 0.6mL, and the concentrations of the hydrogen peroxide and the ammonia water are respectively 1M and 0.8M.
Preferably, the ferroferric oxide nanoenzyme is prepared by the following method: dissolving ferric chloride and trisodium citrate in ethylene glycol, adding anhydrous sodium acetate, stirring for 0.5-2h, reacting at the temperature of 150 ℃ and 200 ℃ for 8-14h, cooling to room temperature, washing with ethanol for multiple times, washing with deionized water for multiple times, and drying at the temperature of 60 ℃ to obtain a black product, namely ferroferric oxide nanoenzyme;
the proportion of the ferric chloride, the trisodium citrate and the anhydrous sodium acetate is 0.325g to 0.2g to 1.2 g.
Preferably, the manganese dioxide nanoenzyme is prepared by the following method: dissolving potassium permanganate and concentrated hydrochloric acid in deionized water, continuously stirring for 0.5-2h, reacting at 120-200 ℃ for 2-24h, cooling to room temperature, washing with ethanol for multiple times, washing with deionized water for multiple times, and drying at 60 ℃ to obtain manganese dioxide nanoenzyme;
the ratio of the potassium permanganate to the concentrated hydrochloric acid is 0.225g to 0.5mL, and the concentration of the concentrated hydrochloric acid is 36-38%.
Preferably, the calcium peroxide is spherical and has a diameter of 70 nm; the manganese dioxide nanoenzyme is in a shape of a nanotube, and the cross section of the manganese dioxide nanoenzyme is 100 x 100 nm; the ferroferric oxide nanoenzyme is spherical and has the diameter of 250 nm.
Preferably, the electrospinning conditions are as follows: the spinning voltage is 15-40kV, the perfusion speed is 0.5-2mL/h, the receiving distance is 10-25cm, and the temperature in the spinning chamber is 15-30 ℃.
Preferably, the drying conditions are: the temperature is 15-30 ℃, the humidity is 10% -25%, and the time is 6-24 h.
The invention also provides a preparation method of the composite nano enzyme concerted catalysis fiber material, which comprises the following steps:
uniformly mixing calcium peroxide, manganese dioxide nanoenzyme, polylactic acid-glycolic acid copolymer and a spinning solvent to obtain a spinning solution A;
step two, uniformly mixing calcium peroxide, ferroferric oxide nanoenzyme, benzoic acid, polylactic acid-glycolic acid copolymer and a spinning solvent to obtain a spinning solution B;
and step three, performing electrostatic spinning on the spinning solution A and the spinning solution B through two parallel spray heads, and drying a product to obtain the composite nano enzyme synergistic catalytic fiber material.
Preferably, in the first step and the second step, the uniform mixing mode is stirring and uniform mixing, and the stirring time is 4-6 h.
The invention also provides application of the composite nano enzyme synergistic catalytic fiber material in preparation of a dressing for promoting wound healing.
Preferably, the wound is a diabetic chronic wound.
As shown in fig. 9 and fig. 10, the principle of the composite nanoenzyme of the present invention synergistically catalyzing the fiber material to promote wound healing is as follows: when the composite nano enzyme is used for synergistically catalyzing the fiber material to be placed on the wound surface of a wound, the calcium peroxide in the composite nano enzyme is subjected to hydrolysis reaction in the presence of wound exudate to generate hydrogen peroxide. Subsequently, two catalytic reactions will occur simultaneously at the wound site: one is that manganese dioxide nano-enzyme with catalase-like activity catalyzes hydrogen peroxide to decompose, generates oxygen and water, and the oxygen can promote the formation of new blood vessels at wounds; in addition, the ferroferric oxide nanoenzyme with peroxidase-like activity participates in catalytic reaction under acidic condition to catalyze the decomposition of hydrogen peroxide to generate hydroxyl free radicals, and the hydroxyl free radicals with strong oxidizing capability can play an effective sterilization role.
Compared with the prior art, the invention has the beneficial effects that:
1. the composite nano enzyme synergistic catalytic fiber material provided by the invention co-spins the spinning solution containing peroxidase-like activity and the spinning solution containing catalase-like activity by using the parallel double spinning nozzles, can efficiently and continuously produce oxygen and hydroxyl free radicals at the same time, so that the catalytic fiber material has the effects of oxygen supply and antibiosis, namely, the hypoxic microenvironment of chronic wounds of diabetes is obviously improved, the formation of new blood vessels is effectively stimulated, the bacterial infection is inhibited, the wound surface infection is prevented, the wound healing is accelerated, particularly the healing of wounds difficult to heal of diabetes, and the catalytic fiber material has the characteristic of absorbing seepage.
2. The composite nano enzyme synergistic catalysis fiber material has the advantages of convenience in use, simplicity in preparation, simplicity in storage and the like, can play a role only by placing the composite nano enzyme synergistic catalysis fiber material at a wound, is convenient for a patient to use compared with the traditional high-pressure oxygen inhalation and local gaseous oxygen inhalation therapy by means of large-scale equipment, reduces the medical cost, overcomes the defects of high storage condition, high clinical use difficulty and the like of hydrogel dressings, is convenient for the patient and medical staff to use, and lays a foundation for clinical application of the hydrogel dressings.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a graph of the results of the oxygen generation capacity of the hybrid fiber of example 2 of the present invention.
FIG. 2 is a graph of the results of the ability of the hybrid fiber of example 3 of the present invention to generate hydroxyl radicals.
FIG. 3 is a scanning electron microscope image of the composite nanoenzyme-co-catalyzed fibrous material of example 4 of the present invention; in the figure, a is a scanning electron microscope image, b is an elemental analysis image, c is an elemental analysis image of Fe, d is an elemental analysis image of Mn, e is an elemental analysis image of Ca, and f is an elemental analysis image of O.
FIG. 4 is a graph showing the results of the ability of the composite nanoenzyme of example 4 of the present invention to synergistically catalyze the production of oxygen from a fibrous material.
FIG. 5 is a graph showing the results of the ability of the composite nanoenzyme of example 4 of the present invention to synergistically catalyze the production of hydroxyl radicals in a fibrous material.
FIG. 6 is a graph showing the results of the antibacterial experiment of the composite nanoenzyme-concerted catalytic fiber material of example 4 of the present invention.
Fig. 7 is a graph showing the results of the mouse diabetic wound model treated with the composite nanoenzyme-concerted catalytic fiber material according to example 4 of the present invention.
Fig. 8 is a graph showing the results of staining the section of the wound surface of the mouse treated with the composite nanoenzyme and the fiber material in example 4 of the present invention.
FIG. 9 is a schematic diagram of the preparation and design of the composite nanoenzyme-concerted catalytic fiber material for promoting wound healing.
Fig. 10 is a schematic diagram of the composite nano-enzyme synergistic catalysis of the fiber material to promote wound healing.
Detailed Description
For the purpose of further illustrating the invention, preferred embodiments of the invention are described below in conjunction with the detailed description, but it is to be understood that these descriptions are only intended to further illustrate the features and advantages of the invention, and not to limit the claims of the invention.
The composite nano enzyme synergistic catalysis fiber material can obviously improve the healing speed of the diabetic chronic wound.
The composite nano enzyme synergistic catalysis fiber material is prepared by electrostatic spinning and drying of spinning solution A and spinning solution B;
the spinning solution A consists of polylactic acid-glycolic acid copolymer (PLGA, an inner dopant A and a spinning solvent, wherein the inner dopant A consists of manganese dioxide nano enzyme and calcium peroxide in a mass ratio of 1 (1-9), the concentration of the polylactic acid-glycolic acid copolymer in the spinning solution A is 5-20 wt%, and the mass ratio of the inner dopant A to the polylactic acid-glycolic acid copolymer is 1: 10;
the spinning solution B consists of polylactic acid-glycolic acid copolymer, an inner admixture B, benzoic acid and a spinning solvent, wherein the inner admixture B consists of ferroferric oxide nanoenzyme and calcium peroxide in a mass ratio of 1 (1-9), the concentration of the polylactic acid-glycolic acid copolymer in the spinning solution B is 5-20 wt%, the concentration of the benzoic acid is 0.5-2 wt%, and the mass ratio of the inner admixture B to the polylactic acid-glycolic acid copolymer is 1: 10.
In the above technical scheme, electrostatic spinning is the prior art, and any method capable of realizing blend spinning of two spinning solutions in the prior art is not particularly limited, and the preferred conditions of electrostatic spinning are as follows: the spinning voltage is 15-40kV, the perfusion speed is 0.5-2mL/h, the receiving distance is 10-25cm, and the temperature in the spinning chamber is 15-30 ℃. The spinning solvent is not particularly limited, and any of the spinning solvents commonly used in the art may be used, and hexafluoroisopropanol is preferable.
In the above technical scheme, the drying conditions are as follows: the temperature is 15-30 ℃, the humidity is 10% -25%, and the time is 6-24 h.
In the above technical solution, the mass ratio of the benzoic acid to the polylactic acid-glycolic acid copolymer is preferably 1: 5.
In the above technical solution, the concentrations of the polylactic acid-glycolic acid copolymer in the spinning solution a and the spinning solution B are preferably 10 wt%, respectively. The polymerization degree of the polylactic acid-glycolic acid copolymer is not particularly limited, and it is preferable that the molecular weight of the polylactic acid-glycolic acid copolymer is 100000Da, and the molar ratio of lactic acid to glycolic acid is 50: 50. The particle sizes of the calcium peroxide, the manganese dioxide nanoenzyme and the ferroferric oxide nanoenzyme are not limited, and the calcium peroxide is preferably spherical and has the diameter of 70 nm; the manganese dioxide nanoenzyme is in a shape of a nanotube, and the cross section of the manganese dioxide nanoenzyme is 100 x 100 nm; the ferroferric oxide nanoenzyme is spherical and has the diameter of 250 nm. Polylactic acid-glycolic acid copolymer, calcium peroxide, manganese dioxide nanoenzyme and ferroferric oxide nanoenzyme are all the prior art and can be obtained by the methods well known to the technical personnel in the field, such as the commercial or laboratory preparation. The present invention provides several preparation methods, but is not limited thereto:
the calcium peroxide is prepared by the following method: fully mixing calcium chloride and polyvinylpyrrolidone in ethanol, carrying out ultrasonic treatment for 0.5-2h, adding ammonia water, continuously stirring for 0.5-2h, then adding hydrogen peroxide at the speed of 0.05-0.2mL/min, continuously stirring until light blue milky solution is obtained, washing with ethanol for multiple times, and drying at 60 ℃ to obtain monodisperse spheres, namely calcium peroxide; wherein, the proportion of calcium chloride, polyvinylpyrrolidone, ammonia water and hydrogen peroxide is as follows: 0.1g to 0.35g to 1mL to 0.6mL, the concentrations of hydrogen peroxide and ammonia water are 1M and 0.8M respectively, ethanol is used as a solvent, and the using amount is not particularly limited;
the ferroferric oxide nano enzyme is prepared by the following method: dissolving ferric chloride and trisodium citrate in ethylene glycol, adding anhydrous sodium acetate, stirring for 0.5-2h, reacting at the temperature of 150 ℃ and 200 ℃ for 8-14h, cooling to room temperature, washing with ethanol for multiple times, washing with deionized water for multiple times, and drying at the temperature of 60 ℃ to obtain a black product, namely ferroferric oxide nanoenzyme; wherein the proportion of the ferric chloride, the trisodium citrate and the anhydrous sodium acetate is as follows: 0.325g to 0.2g to 1.2g, ethylene glycol as a solvent, and the amount is not particularly limited;
the manganese dioxide nano enzyme is prepared by the following method: dissolving potassium permanganate and concentrated hydrochloric acid in deionized water, continuously stirring for 0.5-2h, reacting at 120-200 ℃ for 2-24h, cooling to room temperature, washing with ethanol for multiple times, washing with deionized water, and drying at 60 ℃ to obtain manganese dioxide nanoenzyme; wherein the proportion of the potassium permanganate and the concentrated hydrochloric acid is 0.225g to 0.5mL, the concentration of the concentrated hydrochloric acid is 36 to 38 percent, the deionized water is used as a solvent, and the dosage is not limited specially.
The invention also provides a preparation method of the composite nano enzyme concerted catalysis fiber material, which comprises the following steps:
uniformly mixing calcium peroxide, manganese dioxide nanoenzyme, polylactic acid-glycolic acid copolymer and a spinning solvent to obtain a spinning solution A;
step two, uniformly mixing calcium peroxide, ferroferric oxide nanoenzyme, benzoic acid, polylactic acid-glycolic acid copolymer and a spinning solvent to obtain a spinning solution B;
and step three, performing electrostatic spinning on the spinning solution A and the spinning solution B through two parallel spray heads, and drying a product to obtain the composite nano enzyme synergistic catalytic fiber material.
In the technical scheme, in the first step and the second step, the uniform mixing mode is stirring and mixing uniformly, and the stirring time is 4-6 h.
The invention also provides application of the composite nano enzyme synergistic catalytic fiber material in preparation of a dressing for promoting wound healing. Is especially suitable for promoting wound healing, especially chronic diabetic wound healing. The specific using method comprises the following steps: the dressing is directly applied to the wound surface without special requirements.
In the following examples, various procedures and methods not described in detail are conventional methods well known in the art. Materials, reagents, devices, apparatuses, instruments, apparatuses and the like used in the following examples are commercially available unless otherwise specified.
The terms used in the present invention generally have meanings commonly understood by those of ordinary skill in the art, unless otherwise specified.
The present invention is further illustrated by the following examples.
Example 1
0.1g of calcium chloride and 0.35g of polyvinylpyrrolidone are fully mixed in 15mL of ethanol, ultrasonic treatment is carried out for 0.5h, 1mL of ammonia water (0.8M) is firstly added into the solution, stirring is continuously carried out for 0.5h, then 0.6mL of hydrogen peroxide (1M) is added into the solution at the speed of 0.2mL/min, stirring is continuously carried out until light blue milky solution is obtained, finally, ethanol is used for washing for 3 times, drying is carried out at the temperature of 60 ℃, and the obtained product is monodisperse calcium peroxide spheres with the diameter of 70 nm.
Dissolving 0.325g of ferric chloride and 0.2g of trisodium citrate in 20mL of ethylene glycol, firstly adding 1.2g of anhydrous sodium acetate into the solution, stirring for 0.5h, then adding the obtained mixed solution into a 50mL reaction kettle, continuously heating for 10h at 200 ℃, finally cooling to room temperature, washing for 3 times by using ethanol, then washing for 3 times by using deionized water, and drying at 60 ℃, wherein the obtained black product is spherical ferroferric oxide nanoenzyme with the diameter of 250 nm.
Dissolving 0.225g of potassium permanganate and 0.5mL of concentrated hydrochloric acid in 20mL of deionized water, continuously stirring for 0.5, adding the obtained mixed solution into a 70mL reaction kettle, reacting at 140 ℃ for 12h, cooling to room temperature, washing with ethanol for 3 times, washing with deionized water for 3 times, and drying at 60 ℃ to obtain the product, namely the nano-tubular manganese dioxide nanoenzyme with the cross section of 100 x 100 nm.
Example 2
Step one, dissolving 0.1PLGA (molar ratio of lactic acid to glycolic acid is 50:50, molecular weight is 100000Da) in 0.89g hexafluoroisopropanol to obtain PLGA solution;
step two, mixing the dope with the PLGA solution obtained in the step one according to the mass ratio of the dope to the PLGA being 1:10 to obtain a spinning solution A;
wherein, the inner adulterant consists of manganese dioxide nanoenzyme (prepared in example 1) and calcium peroxide (prepared in example 1) with the mass ratio of 0:10, 1:9, 5:5 and 9: 1;
step three, preparing the hybrid fiber by performing electrostatic spinning and drying on the spinning solution A, wherein the electrostatic spinning conditions are as follows: the spinning voltage is 20kV, the perfusion speed is 0.5mL/h, the receiving distance is 20cm, and the temperature in the spinning chamber is 25 ℃; the drying conditions were: the temperature is 25 ℃, the humidity is 20 percent, and the time is 24 hours.
0.08g of each of the four kinds of hybrid fibers prepared in example 2 was put in a sample cell, 5mL of deionized water was added, and a dissolved oxygen tester was quickly inserted, the system was sealed with a sealing film, and the readings of the dissolved oxygen tester were recorded under magnetic stirring, and the results are shown in FIG. 1. As can be seen from FIG. 1, the oxygen production capacity of the hybrid fiber is influenced by the ratio of manganese dioxide nanoenzyme to calcium peroxide, and when the mass ratio of manganese dioxide nanoenzyme to calcium peroxide is 1:9, the hybrid fiber has the fastest oxygen production rate and the highest oxygen production rate.
Example 3
Step one, dissolving 0.1g of PLGA (molar ratio of lactic acid to glycolic acid is 50:50, molecular weight is 100000Da) in 0.89g of hexafluoroisopropanol to obtain PLGA solution;
step two, mixing the inner dope, benzoic acid and the PLGA solution obtained in the step one to obtain a spinning solution B according to the mass ratio of the inner dope to the PLGA of 1:10 and the mass ratio of the benzoic acid to the polylactic acid-glycolic acid copolymer of 1: 5;
wherein, the inner admixture B consists of ferroferric oxide (prepared in example 1) and calcium peroxide (prepared in example 1) in the mass ratio of 0:10, 1:9, 5:5 and 9: 1;
step three, preparing the hybrid fiber from the spinning solution B through electrostatic spinning and drying, wherein the electrostatic spinning conditions are as follows: the spinning voltage is 20kV, the perfusion speed is 0.5mL/h, the receiving distance is 20cm, and the temperature in the spinning chamber is 25 ℃; the drying conditions were: the temperature is 25 ℃, the humidity is 20 percent, and the time is 24 hours.
0.01g of each of the four hybrid fibers prepared in example 3 was placed in a 5mL glass bottle, 200 μ L of TMB (10mM) and 800 μ L of acetate buffer (pH 4.5) were added thereto, the mixture was magnetically stirred for 20min, and the solution was measured for absorption at 652nm using an ultraviolet-visible absorption spectrometer, and the results are shown in fig. 2. As can be seen from FIG. 2, the hydroxyl radical generating capacity of the hybrid fiber is influenced by the ratio of the ferroferric oxide nanoenzyme to the calcium peroxide, and when the mass ratio of the ferroferric oxide nanoenzyme to the calcium peroxide is 5:5, the absorption value of the solution at 652nm is the highest, which indicates that the hybrid fiber has the strongest capacity of generating hydroxyl radicals.
Example 4
Step one, uniformly mixing 9mg of calcium peroxide, 1mg of manganese dioxide nanoenzyme, 0.1g of polylactic acid-glycolic acid copolymer and 0.89g of hexafluoroisopropanol to obtain spinning solution A;
step two, uniformly mixing 5mg of calcium peroxide, 5mg of ferroferric oxide nanoenzyme, 15mg of benzoic acid, 0.1g of polylactic acid-glycolic acid copolymer and 0.89g of hexafluoroisopropanol to obtain a spinning solution B;
step three, performing electrostatic spinning on the spinning solution A and the spinning solution B through two parallel spray heads, and drying a product to obtain a composite nano enzyme synergistic catalytic fiber material; the conditions of electrostatic spinning are as follows: the spinning voltage is 20kV, the perfusion speed is 0.5/h, the receiving distance is 20cm, and the temperature in the spinning chamber is 25 ℃; the drying conditions were: the temperature is 25 ℃, the humidity is 20 percent, and the time is 24 hours.
4.1 scanning electron microscope observation is carried out on the composite nano enzyme and catalytic fiber material of the example 4.
Fig. 3 is a scanning electron microscope image of the composite nanoenzyme-photocatalytic fiber material prepared in example 4, and it can be seen from fig. 3 that the composite nanoenzyme-photocatalytic fiber material has a uniform fiber structure, and the nanomaterials are considered to be successfully encapsulated in the fibers and have good dispersibility in combination with various metal and oxygen elements shown in elemental analysis.
4.2 the composite nano enzyme prepared in example 4, in coordination with the catalytic fiber material, 0.16g, was placed in a sample cell, 5mL of deionized water was added, and the sample cell was quickly inserted into a dissolved oxygen tester, the system was sealed with a sealing film, and the readings of the dissolved oxygen tester were recorded under magnetic stirring, with the results shown in fig. 4. As can be seen from FIG. 4, the composite nanoenzyme prepared in example 4 synergistically catalyzes the fiber material to have good oxygen production capacity.
4.3 the composite nanoenzyme-co-catalyzed fibrous material 0.2 prepared in example 4 was taken and placed in 5mL glass bottles, respectively, and then 200 μ L of TMB (10mM) and 800 μ L of acetate buffer (pH 4.5) were added, magnetically stirred for 20min, and the absorption of the solution at 652nm was tested using an ultraviolet-visible absorption spectrometer, the results of which are shown in fig. 5. As can be seen from FIG. 5, the composite nano-enzyme prepared in example 4 synergistically catalyzes the fiber material to have good peroxidase activity.
4.4 the composite nano enzyme synergistically catalyzes the killing effect of the fiber material on staphylococcus aureus and escherichia coli.
Preparing an LB culture medium: weighing 2g of tryptone, 2g of sodium chloride and 1g of yeast extract, putting into a conical flask, adding 200mL of deionized water, transferring into a sterilization pot, sterilizing for 20min, and cooling to room temperature for later use.
Preparing a solid LB culture medium and paving a plate: weighing 2g tryptone, 2g sodium chloride, 1g yeast extract and 2.6g agar, placing into a conical flask, adding 200mL deionized water, transferring into a sterilization pot, and sterilizing for 20 min. The culture medium is transferred to a culture dish while the culture medium is hot, and the culture dish is placed in a refrigerator for standby after being cooled.
Escherichia coli (gram-negative bacteria) and staphylococcus aureus (gram-positive bacteria) are respectively used as models to research the antibacterial effect of the composite nano-enzyme synergistic catalytic fiber material. The individual strains were added to Erlenmeyer flasks containing LB medium and cultured at 37 ℃ for 12 hours. Diluting the cultured bacterial liquid by 100 times by using normal saline, transferring 10 mu L of the diluted bacterial liquid to be dripped to a 1cm x 1cm composite nano enzyme synergistic catalytic fiber material, repeatedly washing the fiber material by 990 mu L normal saline for a plurality of times after the fiber material is placed in a closed state for 1h, then transferring 100 mu L of the obtained liquid to an LB solid culture medium, uniformly coating the obtained solid culture medium by using a coater, culturing the obtained solid culture medium at 37 ℃, and taking a picture for recording. The results show that the composite nano enzyme synergistically catalyzes the fiber material to have a strong bactericidal effect on escherichia coli and staphylococcus aureus, which is shown in fig. 6.
4.5 the composite nano enzyme is cooperated to catalyze the fiber material to research the repairing function of the diabetic mouse trauma.
Establishing a mouse diabetes model, performing full-thickness skin excision with a diameter of 8mm on the back of a diabetic mouse, and dripping 30 mu L of 10-contained solution 8 -10 10 CFU mL -1 LB culture solution of staphylococcus aureus. And establishing a diabetic mouse wound infection model. The diabetic mice were divided into two groups, namely a control group and a composite nanoenzyme-catalyzed fibrous material group, each group containing 6 mice. The control group was not treated. The experimental group fixes the 1cm by 1cm composite nano enzyme synergistic catalytic fiber material on the wound surface, changes the composite nano enzyme synergistic catalytic fiber material every day, and observes and records the wound healing condition. The results show that the wound healing effect of the diabetic mice treated by the composite nano-enzyme and the fiber material is obviously better than that of the blank group, and the results are shown in figure 7. Therefore, the composite nano enzyme synergistic catalysis fiber material can obviously promote the healing of diabetic wounds.
4.6 the composite nano enzyme synergistically catalyzes the mechanism of the fiber material for promoting the wound repair of the diabetic mice.
On day 13, wound wounds from 4.5 mice were removed, sectioned, and HE and CD31 stained, with the results shown in fig. 8. As can be seen from fig. 8, the wound surface of the mouse treated by the composite nanoenzyme-synergetic catalytic fiber material recovers better, the epithelial tissue is thicker, and meanwhile, the platelet endothelial cell adhesion molecules are more, which indicates that the composite nanoenzyme-synergetic catalytic fiber material can accelerate the wound healing by promoting the formation of the epithelial tissue and the new blood vessels.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (10)
1. The composite nano enzyme synergistic catalysis fiber material is characterized in that the composite nano enzyme synergistic catalysis fiber material is prepared by spinning a spinning solution A and a spinning solution B through electrostatic spinning and drying;
the spinning solution A consists of a polylactic acid-glycolic acid copolymer, an inner dopant A and a spinning solvent, wherein the inner dopant A consists of manganese dioxide nanoenzyme and calcium peroxide in a mass ratio of 1 (1-9), the concentration of the polylactic acid-glycolic acid copolymer in the spinning solution A is 5-20 wt%, and the mass ratio of the inner dopant A to the polylactic acid-glycolic acid copolymer is 1: 10;
the spinning solution B is composed of a polylactic acid-glycolic acid copolymer, an inner admixture B, benzoic acid and a spinning solvent, wherein the inner admixture B is composed of ferroferric oxide nanoenzyme and calcium peroxide in a mass ratio of 1 (1-9), the concentration of the polylactic acid-glycolic acid copolymer in the spinning solution B is 5-20 wt%, the concentration of the benzoic acid is 0.5-2 wt%, and the mass ratio of the inner admixture B to the polylactic acid-glycolic acid copolymer is 1: 10.
2. The composite nanoenzyme-co-catalyzed fibrous material of claim 1,
in the spinning solution A and the spinning solution B, the concentration of the polylactic acid-glycolic acid copolymer is 10 wt% respectively.
3. The composite nanoenzyme-co-catalyzed fibrous material of claim 1, wherein the spinning solvent is hexafluoroisopropanol;
the molecular weight of the polylactic acid-glycolic acid copolymer is 100000Da, and the molar ratio of lactic acid to glycolic acid is 50: 50.
4. The composite nanoenzyme-co-catalyzed fibrous material of claim 1,
the calcium peroxide is prepared by the following method: fully mixing calcium chloride and polyvinylpyrrolidone in ethanol, carrying out ultrasonic treatment for 0.5-2h, adding ammonia water, continuously stirring for 0.5-2h, then adding hydrogen peroxide at the speed of 0.05-0.2mL/min, continuously stirring until light blue milky solution is obtained, washing with ethanol for multiple times, and drying at 60 ℃ to obtain monodisperse spheres, namely calcium peroxide; the mixture ratio of the calcium chloride to the polyvinylpyrrolidone to the ammonia water to the hydrogen peroxide is 0.1g to 0.35g to 1mL to 0.6mL, and the concentrations of the hydrogen peroxide and the ammonia water are 1M and 0.8M respectively;
the ferroferric oxide nanoenzyme is prepared by the following method: dissolving ferric chloride and trisodium citrate in ethylene glycol, adding anhydrous sodium acetate, stirring for 0.5-2h, reacting at the temperature of 150 ℃ and 200 ℃ for 8-14h, cooling to room temperature, washing with ethanol for multiple times, washing with deionized water for multiple times, and drying at the temperature of 60 ℃ to obtain a black product, namely ferroferric oxide nanoenzyme; the proportion of the ferric chloride, the trisodium citrate and the anhydrous sodium acetate is 0.325g to 0.2g to 1.2 g;
the manganese dioxide nanoenzyme is prepared by the following method: dissolving potassium permanganate and concentrated hydrochloric acid in deionized water, continuously stirring for 0.5-2h, reacting for 2-24h at the temperature of 120-200 ℃, cooling to room temperature, washing for multiple times by using ethanol, washing for multiple times by using deionized water, and drying at the temperature of 60 ℃ to obtain the manganese dioxide nanoenzyme with controllable morphology, wherein the ratio of the potassium permanganate to the concentrated hydrochloric acid is 0.225g to 0.5mL, and the concentration of the concentrated hydrochloric acid is 36-38%.
5. The composite nanoenzyme-co-catalyzed fibrous material of claim 1, wherein the electrospinning conditions are: the spinning voltage is 15-40kV, the perfusion speed is 0.5-2mL/h, the receiving distance is 10-25cm, and the temperature in the spinning chamber is 15-30 ℃.
6. The composite nanoenzyme-concerted catalytic fiber material of claim 1, wherein the drying conditions are: the temperature is 15-30 ℃, the humidity is 10% -25%, and the time is 6-24 h.
7. The method for preparing the composite nano-enzyme co-catalyzed fiber material according to any one of claims 1 to 6, is characterized by comprising the following steps:
uniformly mixing calcium peroxide, manganese dioxide nanoenzyme, polylactic acid-glycolic acid copolymer and a spinning solvent to obtain a spinning solution A;
step two, uniformly mixing calcium peroxide, ferroferric oxide nanoenzyme, benzoic acid, polylactic acid-glycolic acid copolymer and a spinning solvent to obtain a spinning solution B;
and step three, performing electrostatic spinning on the spinning solution A and the spinning solution B through two parallel spray heads, and drying a product to obtain the composite nano enzyme synergistic catalytic fiber material.
8. The method for preparing the composite nano-enzyme and co-catalytic fiber material as claimed in claim 7, wherein in the first step and the second step, the mixing is performed in a manner of stirring and mixing uniformly, and the stirring time is 4-6 h.
9. Use of the composite nanoenzyme of any one of claims 1 to 6 in the concerted catalysis of fibrous material in the manufacture of a dressing for the promotion of wound healing.
10. Use of the composite nanoenzyme-concerted catalytic fibre material of claim 9 in the preparation of a dressing for promoting wound healing, wherein the wound is a diabetic chronic wound.
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Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20090119943A (en) * | 2008-05-18 | 2009-11-23 | (주)고체산소테크 | Oxygen generating diaper and oxygen generating composition thereof |
| US20130287677A1 (en) * | 2010-12-20 | 2013-10-31 | Ocean's King Lighting Science & Technology Co., Ltd. | Preparation method and use of manganese dioxide nano-rod |
| CN107117582A (en) * | 2016-02-24 | 2017-09-01 | 曹荣华 | It is a kind of locally quickly to produce the composition of oxygen |
| CN110384818A (en) * | 2019-07-29 | 2019-10-29 | 河南亚都实业有限公司 | A kind of alginate dressing |
| CN110772379A (en) * | 2019-11-01 | 2020-02-11 | 山东汉方制药有限公司 | Preparation method of composite nanofiber membrane loaded with nanoenzyme and wound surface application thereof |
| CN111588838A (en) * | 2020-05-29 | 2020-08-28 | 扬州大学 | Composition for inhibiting streptococcus mutans and application thereof |
| CN112376124A (en) * | 2020-11-20 | 2021-02-19 | 上海市第六人民医院 | Antibacterial dressing |
| CN112957457A (en) * | 2021-02-05 | 2021-06-15 | 山东大学 | Cascade enzyme-like nano system for promoting diabetic wound healing and preparation method and application thereof |
| WO2021122707A1 (en) * | 2019-12-19 | 2021-06-24 | Solvay Sa | Oxygen generating composition |
| KR20210111576A (en) * | 2020-03-03 | 2021-09-13 | 인하대학교 산학협력단 | Oxygen generating wound covering material and manufacturing method thereof |
| CN114163662A (en) * | 2021-12-16 | 2022-03-11 | 江南大学 | Nano enzyme functionalized hydrogel and preparation method thereof |
| CN114177347A (en) * | 2021-11-03 | 2022-03-15 | 暨南大学 | Antibacterial oxygen release functional gel dressing and preparation and application thereof |
-
2022
- 2022-04-21 CN CN202210420339.1A patent/CN114832831B/en active Active
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20090119943A (en) * | 2008-05-18 | 2009-11-23 | (주)고체산소테크 | Oxygen generating diaper and oxygen generating composition thereof |
| US20130287677A1 (en) * | 2010-12-20 | 2013-10-31 | Ocean's King Lighting Science & Technology Co., Ltd. | Preparation method and use of manganese dioxide nano-rod |
| CN107117582A (en) * | 2016-02-24 | 2017-09-01 | 曹荣华 | It is a kind of locally quickly to produce the composition of oxygen |
| CN110384818A (en) * | 2019-07-29 | 2019-10-29 | 河南亚都实业有限公司 | A kind of alginate dressing |
| CN110772379A (en) * | 2019-11-01 | 2020-02-11 | 山东汉方制药有限公司 | Preparation method of composite nanofiber membrane loaded with nanoenzyme and wound surface application thereof |
| WO2021122707A1 (en) * | 2019-12-19 | 2021-06-24 | Solvay Sa | Oxygen generating composition |
| KR20210111576A (en) * | 2020-03-03 | 2021-09-13 | 인하대학교 산학협력단 | Oxygen generating wound covering material and manufacturing method thereof |
| CN111588838A (en) * | 2020-05-29 | 2020-08-28 | 扬州大学 | Composition for inhibiting streptococcus mutans and application thereof |
| CN112376124A (en) * | 2020-11-20 | 2021-02-19 | 上海市第六人民医院 | Antibacterial dressing |
| CN112957457A (en) * | 2021-02-05 | 2021-06-15 | 山东大学 | Cascade enzyme-like nano system for promoting diabetic wound healing and preparation method and application thereof |
| CN114177347A (en) * | 2021-11-03 | 2022-03-15 | 暨南大学 | Antibacterial oxygen release functional gel dressing and preparation and application thereof |
| CN114163662A (en) * | 2021-12-16 | 2022-03-11 | 江南大学 | Nano enzyme functionalized hydrogel and preparation method thereof |
Non-Patent Citations (4)
| Title |
|---|
| MINGHAN HU ET AL: "Fibrous Nanozyme Dressings with Catalase-Like Activity for H2O2 Reduction To Promote Wound Healing", ACS APPL. MATER. INTERFACES, vol. 9 * |
| QIAN WANG ET AL: "Multifunctional hydrogel platform for biofilm scavenging and O2 generating with photothermal effect on diabetic chronic wound healing", JOURNAL OF COLLOID AND INTERFACE SCIENCE, vol. 617 * |
| XIONG ZHOU ET AL: "Infection Micromilieu-Activated Nanocatalytic Membrane for Orchestrating Rapid Sterilization and Stalled Chronic Wound Regeneration", ADVANCED FUNCTIONAL MATERIALS, vol. 32 * |
| 裴大婷等: "组织工程用局部释氧材料的研究进展", 临床医学工程, vol. 25 * |
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