CN114470297A - Sugar-triggered response type wound quick-healing dressing and preparation method thereof - Google Patents

Sugar-triggered response type wound quick-healing dressing and preparation method thereof Download PDF

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CN114470297A
CN114470297A CN202111562405.0A CN202111562405A CN114470297A CN 114470297 A CN114470297 A CN 114470297A CN 202111562405 A CN202111562405 A CN 202111562405A CN 114470297 A CN114470297 A CN 114470297A
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sugar
nanoenzyme
dressing
hydrogel
wound
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CN114470297B (en
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李利平
张瑞平
白佩蓉
杜宝洁
杨杰
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Shanxi Medical University
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    • A61L15/00Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/22Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing macromolecular materials
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Abstract

The invention discloses a sugar-triggered response type wound quick-healing dressing and a preparation method thereof, wherein the dressing comprises an antibacterial white sheet and a repairing black sheet which are sequentially used, the antibacterial white sheet is a sugar-triggered response type wound antibacterial dressing, and the repairing black sheet is a sugar-triggered response type wound quick-healing dressing; the purposes of integrating four functions of controlling sugar, cleaning wounds, diminishing inflammation, improving microcirculation and protecting wound surfaces are realized by sequentially using the antibacterial white tablets and the repairing black tablets; the preparation method comprises the following steps: uniformly mixing sodium alginate, hyaluronic acid and polyethylene glycol, adding multifunctional nano enzyme, uniformly mixing, adding a cross-linking agent and a curing agent, and molding in a mold to obtain hydrogel; covering the formed hydrogel with release paper or carbon fiber-like fabric, and attaching dressing fiber.

Description

Sugar-triggered response type wound quick-healing dressing and preparation method thereof
Technical Field
The invention discloses a sugar-triggered response type wound quick-healing dressing and a preparation method thereof, and relates to the technical field of nano-catalysis technology, broad-spectrum antibiosis, wound quick-healing and medical dressing preparation.
Background
Diabetic Foot Ulcers (DFUs) are a devastating disease in many diabetics with an increasing prevalence and incidence. The complex pathophysiology of the DFU wound environment makes finding effective treatments difficult. Current treatments for DFU include debridement, infection control, maintaining a moist wound environment, and reduced pressure. Despite these interventions, a large number of DFUs remain incurable, with annual costs exceeding $ 310 million. Topical biomaterial hydrogels have been developed to implement new therapeutic approaches to enhance therapeutic efficacy and are advantageous for their ease of application, adjustability and ability to improve therapeutic release characteristics.
Because the diabetic is in a high-sugar environment for a long time, the wound surface is susceptible to bacteria, and the lower limbs are easy to generate blood vessels and neuropathy, the wound surface has poor repairing capability, the pain sensation of the patient is not sensitive, and repeated injury is easy to cause. Therefore, the diabetic foot wound is extremely difficult to repair, and one diabetic foot amputates every 20 seconds in the world. The existing sugar foot dressing on the market is composed of a layer of non-woven fabric and epidermal growth factors or directly uses cotton, gauze, bandages and the like to act on wounds, and the principle of the dressing is mainly that the dressing absorbs exudates such as wound blood and the like to achieve the purpose of controlling infection. When necessary, the whole body system treatment must be carried out by matching with hypoglycemic drugs. At present, a material which can completely solve the problem of wound healing is not found, and the technologies of sugar control, debridement and inflammation diminishing and wound healing fast are still in bottleneck.
Disclosure of Invention
The invention overcomes the defects in the prior art, and aims to solve the technical problem of providing a sugar-triggered response type wound quick-healing dressing and a preparation method thereof, so as to achieve the purposes of integrating four functions of sugar control, debridement and inflammation diminishing, microcirculation improving and wound surface protecting.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
the sugar-triggered response type wound quick-healing dressing comprises an antibacterial white sheet and a repairing black sheet which are used sequentially, wherein the antibacterial white sheet is a sugar-triggered response type wound antibacterial dressing, and the repairing black sheet is a sugar-triggered response type wound quick-healing dressing.
A preparation method of a sugar-triggered response type wound quick-healing dressing comprises the following steps:
preparing an antibacterial white tablet:
step 1) firstly, uniformly mixing sodium alginate, hyaluronic acid and polyethylene glycol to obtain a dispersion liquid I;
step 2) adding the multifunctional nano enzyme I into the dispersion liquid I, and uniformly mixing to obtain a dispersion liquid II;
step 3) adjusting the pH of the dispersion liquid II to be in a weak acid range, adding a cross-linking agent and a curing agent into the dispersion liquid II, and then standing and forming in a mold to obtain a hydrogel I containing the multifunctional nano enzyme I;
step 4) covering release paper on one side of the formed hydrogel, and attaching dressing fibers (materials with certain waterproof function and good air permeability such as non-woven fabrics, melt-blown fabrics and GORE-TEX waterproof and breathable fabrics) on the other side of the hydrogel for covering to obtain an antibacterial white sheet, namely the sugar-triggered response type wound antibacterial dressing;
preparation of the repair black tablets:
step a), firstly, uniformly mixing sodium alginate, hyaluronic acid and polyethylene glycol to obtain a dispersion liquid A;
step B), adding multifunctional nano enzyme A and nutrient substances (such as stem cell extract, epidermal growth factors and the like) into the dispersion liquid A, and uniformly mixing to obtain a dispersion liquid B;
step c) adjusting the pH value of the dispersion liquid B to be in a neutral to alkalescent range, adding a cross-linking agent and a curing agent into the dispersion liquid B, and then standing and forming in a mold to obtain hydrogel II;
and d) adding a carbon fiber-like braided fabric on the hydrogel II, and attaching dressing fibers (comprising a layer of non-woven fabric or GORE-TEX fabric and other materials with waterproof function and good air permeability) to the outer surface of the carbon fiber-like braided fabric to obtain a repairing black sheet, namely the sugar-triggered response type wound rapid repairing dressing.
Further, the multifunctional nanoenzyme I in the hydrogel I comprises a glucose-like oxidase (or glucose-oxidizing nanoenzyme) and a peroxidase nanoenzyme; the multifunctional nanoenzyme A in the hydrogel II comprises superoxide dismutase-like nanoenzyme and hydrogen peroxide-like nanoenzyme.
Further, in the hydrogel I, the mass percent of sodium alginate is 2-6%, the mass percent of hyaluronic acid is 0.8-5%, the mass percent of polyethylene glycol is 0.1-0.6%, the mass percent of multifunctional nano-enzyme I is 0.004-0.4% (wherein the mass percent of the glucose-like oxidase is 0.002-0.2%, the mass percent of the peroxidase nano-enzyme is 0.002-0.2%), the mass percent of the cross-linking agent is 0.1-0.6%, and the mass percent of the curing agent is 0.1-0.5%;
in the hydrogel II, the mass percent of sodium alginate is 2-6%, the mass percent of hyaluronic acid is 0.8-5%, the mass percent of polyethylene glycol is 0.1-0.6%, the mass percent of multifunctional nano enzyme A is 0.001-0.5%, the mass percent of cross-linking agent is 0.1-0.6%, and the mass percent of curing agent is 0.1-0.5%.
Further, the pH value of the dispersion liquid II is adjusted to be in a weakly acidic range from 4.0 to 6.0 in the step 3), and the pH value of the dispersion liquid B is adjusted to be in a weakly alkaline range from 7.0 to 8.0 in the step c).
Further, the hydrogel crosslinking agent comprises at least one of tetramethylethylenediamine, 1, 4-butanediol diglycidyl ether, oxalic acid dihydrazide, polyethylene glycol, glutaraldehyde and divinyl sulfone; the curing agent includes a divalent metal cation such as Ba2+、Sr2+、Ca2+、Pb2+、Cu2+、Cd2+、Co2+、Ni2+、Zn2+And Mn2+At least one of (1).
Further, the carbon fibers in the carbon-like fiber braided fabric are activated carbon fibers or high-strength carbon fibers.
Furthermore, the weaving method of the carbon fiber-like woven fabric comprises plain weave, twill weave and satin weave, and mainly comprises 1k, 3k and 6 k.
Furthermore, the strong absorption and permeation performance of the carbon fibers in the carbon fiber-like braided fabric can absorb seepage by regulating the specific surface area and the pore size distribution of the activated carbon fibers and also by regulating the braiding density of the carbon fibers and utilizing the siphon effect of carbon fiber gaps.
Further, the multifunctional nanoenzyme I and the multifunctional nanoenzyme A comprise at least one of metal nanoenzyme, metal oxide nanoenzyme, nonmetal nanoenzyme, hybrid nanoenzyme or monatomic enzyme.
Further, the metal nano enzyme is formed by metal simple substances of Au, Ag, Pt, Pd, Rh, Ru, Fe, Co, Ni, Cu or Mn; the nonmetal nanoenzyme is carbide, nitride, phosphide, boride or carbon quantum dot nanoenzyme.
The sugar-triggered response wound quick-healing dressing is a quick-healing dressing integrating four functions of sugar control, debridement and inflammation diminishing of a diabetic foot ulcer wound surface, microcirculation improvement and wound surface protection.
Compared with the prior art, the invention has the following beneficial effects:
(1) according to the sugar-triggered response wound quick-healing dressing provided by the invention, sugar in a wound surface environment is effectively controlled by glucose oxidase in a slightly acidic environment, so that the effect of 'preparing sugar by sugar' is achieved, hydrogen peroxide required in an antibacterial process can be generated in the process, the hydrogen peroxide is decomposed into active oxygen by catalase-like enzyme, and the effect of efficient sterilization is achieved. Then, in a neutral environment, the nano enzyme reacts with endogenous hydrogen peroxide through cascade catalysis to generate oxygen required by the rapid healing of the wound surface, and the aims of controlling sugar, cleaning wound, diminishing inflammation, improving microcirculation and protecting the wound surface are fulfilled by sequentially using the antibacterial white tablets and the repair black tablets.
(2) The sugar-triggered response wound quick-healing dressing prepared by the invention effectively fixes bacteria at the wound and prevents the invasion of the bacteria through long-term adhesion, thereby protecting the wound. The hydrogel can keep the local moisture of the wound, accelerate the healing of the wound and absorb a small amount of seepage.
(3) The preparation method provided by the invention has the advantages of low raw material cost, simple process, short experimental period, mild preparation conditions, capability of being operated at room temperature, no external stimulation, no toxic substance generation, environmental friendliness and easiness in batch production.
Drawings
FIG. 1 shows the production of H by glucose oxidase produced by the method of example 12O2And (4) an activity diagram.
Fig. 2 is a scanning electron microscope image of the carbon fiber fabric and the carbon fiber used in example 2 of the present invention.
FIG. 3 is a scanning electron micrograph of the anti-inflammatory repair-promoting hydrogel used in example 2 of the present invention.
FIG. 4 is a CAT-like activity diagram of Mn-based nanoenzymes prepared in example 3 of the present invention.
Detailed Description
The invention will be further explained with reference to the drawings.
Example 1
Preparation and characterization of sugar-triggered response type Mn-based nano enzyme wound antibacterial dressing (antibacterial white sheet)
Firstly, 4g of sodium alginate is dissolved in 100ml of water to obtain a 4 wt% sodium alginate aqueous solution, then 2g of hyaluronic acid is added, and the solution is heated and dissolved to obtain 100ml of mixed solution. And adding polyethylene glycol into the mixed solution for crosslinking, wherein the mass ratio of the polyethylene glycol to the sodium alginate is 1: 20, removing bubbles in vacuum. Adding 20mg of glucose oxidation nano-enzyme and 15mg of Mn nano-enzyme into the mixed solution, and carrying out N reaction at room temperature2Stirring for 12 h. At the same time, the pH of the solution is adjusted to between 4.5 and 5.5 using phosphate buffer and excess water is removed in two steps by ultrafiltration. Then 0.2g of cross-linking agent and 0.1g of curing agent are added, the mixture is kept stand and formed in a mould, the mixture is kept stand for 10min at room temperature to obtain sugar-triggered response type wound antibacterial hydrogel, and then release paper and non-woven fabric are used for coating the hydrogel to prepare the sugar-triggered response type Mn-based nano enzyme antibacterial dressing (namely the 'antibacterial white sheet').
FIG. 1 shows a grape used in this exampleProduction of H by sugar oxidation nano enzyme2O2And (4) an activity diagram. As can be seen from the figure, the glucose oxidation nano-enzyme has good H production2O2The ability of the cell to perform.
Example 2
Preparation and characterization of sugar-triggered response type Fe-based nanoenzyme wound repair dressing (repairing black sheet)
First, 3g of sodium alginate was dissolved in 100ml of water to obtain a 3 wt% sodium alginate aqueous solution, and then 3g of hyaluronic acid was added thereto and dissolved by heating to obtain 100ml of a mixed solution. Adding polyethylene glycol into the mixed solution for crosslinking, wherein the mass ratio of the polyethylene glycol to the sodium alginate is 1: and 15, removing bubbles in vacuum. 10mg of Fe3O4Adding the nano enzyme into the mixed solution at room temperature under N2Stirring for 12 h. At the same time, the pH of the solution is adjusted to between 7.0 and 7.5 using phosphate buffer and excess water can be removed in two steps by ultrafiltration. Then 0.1g of cross-linking agent and 0.2g of curing agent are added, and the mixture is kept stand in a mould for forming and is kept stand for 10min at room temperature, so that the hydrogel for resisting inflammation and promoting repair is obtained. The outer side of the hydrogel is attached with carbon fiber fabric, and the carbon fiber fabric is coated by release paper and non-woven fabric to prepare the sugar-triggered response type Fe-based nanoenzyme wound repair dressing (namely the 'repair black sheet'). In this example, Fe3O4The nano enzyme has the activity of both superoxide dismutase-like and catalase-like.
Fig. 2 is a scanning electron microscope image of the carbon fiber fabric and the carbon fibers. It can be seen from the figure that the carbon fiber fabric adopts a plain weave method, the outer layer of the carbon fiber fabric is white and is non-woven fabric, the carbon fiber fabric has strong absorption and permeation performance by regulating the specific surface area and the pore size distribution of the activated carbon fiber, and seepage can be absorbed by utilizing the siphon effect of carbon fiber gaps by regulating the weaving density of the carbon fiber. The carbon fiber has a diameter of about 5 μm and a smooth surface. FIG. 3 is a scanning electron micrograph of an anti-inflammatory repair-promoting hydrogel. The figure shows that the hydrogel is a porous reticular structure, which is beneficial to protecting the wound surface and absorbing the wound surface seepage.
Example 3
Preparation and characterization of sugar-triggered response type Mn-based nanoenzyme wound repair dressing (repairing black sheet)
First, 3g of sodium alginate was dissolved in 100ml of water to obtain a 3 wt% sodium alginate aqueous solution, and then 4g of hyaluronic acid was added thereto and dissolved by heating to obtain 100ml of a mixed solution. Adding polyethylene glycol into the mixed solution for crosslinking, wherein the mass ratio of the polyethylene glycol to the sodium alginate is 1: and 18, removing bubbles in vacuum. Adding 15mg of Mn nanoenzyme into the mixed solution, and performing N reaction at room temperature2Stirring for 12 h. At the same time, the pH of the solution is adjusted to between 7.0 and 7.8 using phosphate buffer and excess water can be removed in two steps by ultrafiltration. Then 0.2g of cross-linking agent and 0.25g of curing agent are added, and the mixture is kept stand in a mould for forming and is kept stand for 10min at room temperature, so that the hydrogel for resisting inflammation and promoting repair is obtained. The outer side is attached with carbon fiber fabric, and the carbon fiber fabric is coated by release paper and non-woven fabric to prepare the sugar-triggered response type Mn-based nanoenzyme wound repair dressing ('repair black sheet').
FIG. 4 is a CAT-like activity diagram of Mn-based nanoenzymes. The graph shows that the Mn-based nanoenzyme has excellent CAT-like activity, can generate a large amount of oxygen and provides sufficient oxygen for wound repair.
Example 4
Preparation of sugar-triggered response type Pt-based nanoenzyme wound repair dressing (black repair patch)
First, 3g of sodium alginate was dissolved in 100ml of water to obtain a 3 wt% sodium alginate aqueous solution, and then 4g of hyaluronic acid was added thereto and dissolved by heating to obtain 100ml of a mixed solution. Adding polyethylene glycol into the mixed solution for crosslinking, wherein the mass ratio of the polyethylene glycol to the sodium alginate is 1: 20, removing bubbles in vacuum. Adding 20mg of Pt-based nanoenzyme into the mixed solution, and performing N reaction at room temperature2Stirring for 12 h. At the same time, the pH of the solution is adjusted to between 7.0 and 8.0 using phosphate buffer and excess water can be removed in two steps by ultrafiltration. Then 0.3g of cross-linking agent and 0.2g of curing agent are added, and the mixture is kept stand in a mould for forming and is kept stand for 10min at room temperature, so that the hydrogel for resisting inflammation and promoting repair is obtained. The carbon fiber fabric is attached to the outer side of the wound repairing dressing, and the wound repairing dressing is coated by release paper and non-woven fabric to prepare the sugar-triggered response type Pt-based nanoenzyme wound repairing dressing ('repairing black sheet').
Example 5
Preparation of sugar-triggered response type Mn-based nanoenzyme wound repair dressing (repairing black sheet)
Firstly, 2g of sodium alginate is dissolved in 100ml of water to obtain a 2 wt% sodium alginate aqueous solution, then 5g of hyaluronic acid is added, and the solution is heated and dissolved to obtain 100ml of mixed solution. 0.1g of polyethylene glycol was added to the mixed solution for crosslinking, and bubbles were removed in vacuo. Adding 0.5g of Mn nanoenzyme into the mixed solution, and performing N reaction at room temperature2Stirred for 11 h. At the same time, the pH of the solution is adjusted to between 7.0 and 7.3 using phosphate buffer and excess water can be removed in two steps by ultrafiltration. Then 0.3g of cross-linking agent and 0.4g of curing agent are added, and the mixture is kept stand in a mould for forming and is kept stand for 10min at room temperature, so that the hydrogel for resisting inflammation and promoting repair is obtained. The outer side is attached with carbon fiber fabric, and the carbon fiber fabric is coated by release paper and non-woven fabric to prepare the sugar-triggered response type Mn-based nanoenzyme wound repair dressing ('repair black sheet').
Example 6
Preparation of sugar-triggered response type Mn-based nanoenzyme wound repair dressing (repairing black sheet)
Firstly 6g of sodium alginate is dissolved in 100ml of water to obtain a 6 wt% sodium alginate aqueous solution, then 4g of hyaluronic acid is added, and the solution is heated and dissolved to obtain 100ml of mixed solution. 0.6g of polyethylene glycol was added to the mixed solution for crosslinking, and bubbles were removed in vacuo. Adding 0.001g of Mn nanoenzyme into the mixed solution, and performing N reaction at room temperature2Stirring for 14 h. At the same time, the pH of the solution is adjusted to between 7.0 and 7.4 using phosphate buffer and excess water can be removed in two steps by ultrafiltration. Then 0.6g of cross-linking agent and 0.5g of curing agent are added, and the mixture is kept stand in a mould for forming and is kept stand for 15min at room temperature, so that the hydrogel for resisting inflammation and promoting repair is obtained. The outer side of the wound repairing dressing is attached with carbon fiber fabric, and the wound repairing dressing is coated by release paper and GORE-TEX fabric to prepare the sugar-triggered response type Mn-based nanoenzyme wound repairing dressing ('repairing black sheet').
Example 7
Preparation of sugar-triggered response type Mn-based nanoenzyme wound repair dressing (repairing black sheet)
Firstly, 2g of sodium alginate is dissolved in 100ml of water to obtain a 2 wt% sodium alginate aqueous solution, then 0.8g of hyaluronic acid is added, and the solution is heated and dissolved to obtain 100ml of mixed solution.0.1g of polyethylene glycol was added to the mixed solution for crosslinking, and bubbles were removed in vacuo. Adding 0.002g of Mn nanoenzyme into the mixed solution, and performing N reaction at room temperature2Stirring for 10 h. At the same time, the pH of the solution is adjusted to between 7.0 and 7.3 using phosphate buffer and excess water can be removed in two steps by ultrafiltration. Then 0.1g of cross-linking agent and 0.1g of curing agent are added, and the mixture is kept stand in a mould for forming and is kept stand for 10min at room temperature, so that the hydrogel for resisting inflammation and promoting repair is obtained. The outer side is attached with carbon fiber fabric, and the carbon fiber fabric is coated by release paper and non-woven fabric to prepare the sugar-triggered response type Mn-based nanoenzyme wound repair dressing ('repair black sheet').
Example 7
Preparation of sugar-triggered response type Mn-based nano enzyme wound antibacterial dressing (antibacterial white sheet)
Firstly 6g of sodium alginate is dissolved in 100ml of water to obtain a 6 wt% sodium alginate aqueous solution, then 5g of hyaluronic acid is added, and the solution is heated and dissolved to obtain 100ml of mixed solution. Adding polyethylene glycol into the mixed solution for crosslinking, wherein the mass ratio of the polyethylene glycol to the sodium alginate is 1: 4, removing bubbles in vacuum. Adding 200mg of glucose oxidation nano-enzyme and 150mg of Mn nano-enzyme into the mixed solution, and carrying out N reaction at room temperature2Stirring for 12 h. At the same time, the pH of the solution is adjusted to between 4.0 and 5.0 using phosphate buffer and excess water can be removed in two steps by ultrafiltration. Then adding 0.1g of cross-linking agent and 0.5g of curing agent, standing and forming in a mould, standing for 13min at room temperature to obtain sugar-triggered response type wound antibacterial hydrogel, and then coating the hydrogel by release paper and non-woven fabric to prepare the sugar-triggered response type Mn-based nano enzyme antibacterial dressing (namely the 'antibacterial white sheet').
Example 8
Preparation of sugar-triggered response type Mn-based nano enzyme wound antibacterial dressing (antibacterial white sheet)
Firstly, 2g of sodium alginate is dissolved in 100ml of water to obtain a 2 wt% sodium alginate aqueous solution, then 0.8g of hyaluronic acid is added, and the mixture is heated and dissolved to obtain 100ml of mixed solution. Adding polyethylene glycol into the mixed solution for crosslinking, wherein the mass ratio of the polyethylene glycol to the sodium alginate is 1: and (30) removing bubbles in vacuum. Oxidizing 100mg of glucose with nanoenzyme and 100mg of MAdding N nano enzyme into the mixed solution, and performing N reaction at room temperature2Stirring for 10 h. At the same time, the pH of the solution is adjusted to between 5.0 and 6.0 using phosphate buffer and excess water can be removed in two steps by ultrafiltration. Then adding 0.1g of cross-linking agent and 0.5g of curing agent, standing and forming in a mould, standing for 15min at room temperature to obtain sugar-triggered response type wound antibacterial hydrogel, and then coating the hydrogel by release paper and non-woven fabric to prepare the sugar-triggered response type Mn-based nano enzyme antibacterial dressing (namely the 'antibacterial white sheet').
According to the sugar-triggered response wound quick-healing dressing provided by the invention, sugar in a wound surface environment is effectively controlled by glucose oxidase in a slightly acidic environment, so that the effect of 'preparing sugar by sugar' is achieved, hydrogen peroxide required in an antibacterial process can be generated in the process, the hydrogen peroxide is decomposed into active oxygen by catalase-like enzyme, and the effect of efficient sterilization is achieved. Then, in a neutral environment, the nano enzyme reacts with endogenous hydrogen peroxide to generate oxygen required by the rapid healing of the wound surface through cascade catalysis, in actual use, an antibacterial white sheet is applied to the wound, a repairing black sheet is applied after a certain time, and the aims of integrating four functions of sugar control, debridement and inflammation diminishing, microcirculation improvement and wound surface protection are achieved through the antibacterial white sheet and the repairing black sheet which are sequentially used.
Three key technologies are provided in the scheme of the invention to realize four effects of diabetic foot healing. Glucose is catalyzed in situ to generate active species through a sugar triggering response technology, so that the effects of reducing blood sugar and broad-spectrum antibiosis are achieved; by adopting a wound microenvironment regulation and control technology, carbon molecules form Brownian motion after carbon fibers are electrified, electric energy is converted into far infrared rays, and blood circulation is improved; the infection defense system is rebuilt by oxygen generated by sugar triggering; in the repair stage, biologically extracted antioxidant is used for eliminating local redundant free radicals and accelerating wound healing; the bionic hydrogel preparation technology can keep the moist environment of the wound surface, the bionic mussel characteristic can realize the characteristics of repeated pasting and repeated utilization, and the micro acid hydrogel can further improve the sugar triggering catalysis efficiency. The antibacterial performance and the repairing performance of the nano enzyme are changed as required by regulating the pH environment of the hydrogel. The glucose oxidation nano enzyme in the glucose control stage oxidizes glucose on the wound surface of a patient into gluconic acid and hydrogen peroxide, and then the hydrogen peroxide is catalyzed by a peroxidase-like enzyme to generate hydroxyl radical active species with strong oxidation activity for broad-spectrum antibiosis, so that the dual purposes of reducing the glucose and resisting the bacteria are achieved. The reaction can be effectively enhanced by regulating the pH of the hydrogel. In the repair stage, the pH of the hydrogel is regulated to convert the characteristics of the loaded nano enzyme from antibiosis to repair, the catalase-like characteristics are shown, and oxygen is generated. In addition, the hydrogel is also loaded with stem cell extract, which provides nutrient substances for the wound surface. The carbon fibers in the black sheet are used as good conductors, local blood circulation is promoted by the micro-current stimulation and the far infrared radiation performance under the condition of electrifying, the reconstruction of new tissue of the wound surface is promoted, the microcirculation is improved, in addition, hydrogel provides a moist environment for the wound surface, the collagen deposition and angiogenesis are promoted together, and the effect of protecting the wound surface is achieved.
In conclusion, the glucose oxidase, the nano enzyme with various enzyme activities, the carbon fiber and the self-adhesive hydrogel are compounded together to be used for the rapid healing of the wound surface of the diabetic foot, so that the glucose oxidase, the nano enzyme with various enzyme activities, the carbon fiber and the self-adhesive hydrogel can show remarkable sugar control and antibacterial properties, can also show the functions of debridement, inflammation diminishing and microcirculation improvement, and provides rich oxygen and humid environment for the healing of the wound surface, thereby protecting the wound surface, promoting collagen deposition and angiogenesis, and remarkably accelerating the skin reconstruction.
The sugar-triggered response wound quick-healing dressing prepared by the invention effectively fixes bacteria at the wound and prevents the invasion of the bacteria through long-term adhesion, thereby protecting the wound. The hydrogel can keep the local moisture of the wound, accelerate the healing of the wound and absorb a small amount of seepage.
The preparation method provided by the invention has the advantages of low raw material cost, simple process, short experimental period, mild preparation conditions, capability of being operated at room temperature, no external stimulation, no toxic substance generation, environmental friendliness and easiness in batch production.
It is noted that the term "comprises/comprising" or any other similar term is intended to cover a non-exclusive inclusion, such that a process, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, article, or apparatus/device.
The embodiments of the present invention have been described in detail, but the present invention is not limited to the above embodiments, and various changes can be made without departing from the gist of the present invention within the knowledge of those skilled in the art.

Claims (9)

1. The sugar-triggered response type wound quick-healing dressing is characterized by comprising an antibacterial white sheet and a repairing black sheet which are sequentially used, wherein the antibacterial white sheet is a sugar-triggered response type wound antibacterial dressing, and the repairing black sheet is a sugar-triggered response type wound quick-healing dressing.
2. The preparation method of the sugar-triggered response type wound quick-healing dressing disclosed by claim 1, which is characterized by comprising the following steps of:
preparing an antibacterial white tablet:
step 1) firstly, uniformly mixing sodium alginate, hyaluronic acid and polyethylene glycol to obtain a dispersion liquid I;
step 2) adding the multifunctional nano enzyme I into the dispersion liquid I, and uniformly mixing to obtain a dispersion liquid II;
step 3) adding a cross-linking agent and a curing agent into the dispersion liquid II, and then standing and forming in a mold to obtain a hydrogel I containing the multifunctional nano enzyme I;
step 4) covering release paper on one side of the formed hydrogel, and attaching dressing fiber on the other side of the formed hydrogel for covering to obtain an antibacterial white sheet, namely the sugar-triggered response type wound antibacterial dressing;
preparation of the repair black tablets:
step a), firstly, uniformly mixing sodium alginate, hyaluronic acid and polyethylene glycol to obtain a dispersion liquid A;
step B), adding the multifunctional nano enzyme A and nutrient substances into the dispersion liquid A, and uniformly mixing to obtain a dispersion liquid B;
step c) adding a cross-linking agent and a curing agent into the dispersion liquid B, and then standing and forming in a mold to obtain hydrogel II;
and d) adding a carbon-like fiber braided fabric on the hydrogel II, and attaching dressing fiber to the outer surface of the carbon-like fiber braided fabric to obtain a repairing black sheet, namely the sugar-triggered response type wound rapid repairing dressing.
3. The preparation method of the sugar-triggered response wound quick-healing dressing as claimed in claim 2, wherein the multifunctional nanoenzyme I in the hydrogel I comprises a glucose-like oxidase nanoenzyme and a peroxidase nanoenzyme; the multifunctional nanoenzyme A in the hydrogel II comprises superoxide dismutase-like nanoenzyme and hydrogen peroxide-like nanoenzyme.
4. The preparation method of the sugar-triggered response wound quick-healing dressing according to claim 3, wherein in the hydrogel I, the mass percent of sodium alginate is 2-6%, the mass percent of hyaluronic acid is 0.8-5%, the mass percent of polyethylene glycol is 0.1-0.6%, the mass percent of multifunctional nanoenzyme I is 0.004-0.4%, the mass percent of cross-linking agent is 0.1-0.6%, the mass percent of curing agent is 0.1-0.5%, and the mass percent of solvent is H2O;
In the hydrogel II, the mass percent of sodium alginate is 2-6%, the mass percent of hyaluronic acid is 0.8-5%, the mass percent of polyethylene glycol is 0.1-0.6%, the mass percent of multifunctional nano enzyme A is 0.001-0.5%, the mass percent of cross-linking agent is 0.1-0.6%, the mass percent of curing agent is 0.1-0.5%, and the mass percent of solvent is H2O。
5. The method for preparing a sugar-triggered responsive wound healing dressing according to claim 2, wherein the hydrogel cross-linking agent comprises at least one of tetramethylethylenediamine, 1, 4-butanediol diglycidyl ether, oxalic acid dihydrazide, polyethylene glycol, glutaraldehyde and divinyl sulfone; the curing agent includes a divalent metal cation such as Ba2+、Sr2+、Ca2+、Pb2+、Cu2+、Cd2+、Co2+、Ni2+、Zn2+And Mn2+At least one of (1).
6. The method for preparing the sugar-triggered responsive wound quick-healing dressing as claimed in claim 2, wherein the carbon fibers in the carbon-like fiber braided fabric are activated carbon fibers or high-strength carbon fibers.
7. The method for preparing the sugar-triggered responsive wound quick-healing dressing according to claim 2, wherein the weaving method of the carbon fiber-like woven fabric comprises plain weave, twill weave and satin weave, and the types of the carbon fiber-like woven fabric comprise 1k, 3k and 6 k.
8. The method for preparing the sugar-triggered response wound quick-healing dressing as claimed in claim 2, wherein the multifunctional nanoenzyme I and the multifunctional nanoenzyme A comprise at least one of metal nanoenzyme, metal oxide nanoenzyme, nonmetal nanoenzyme, hybrid nanoenzyme or monatin enzyme.
9. The preparation method of the sugar-triggered response wound quick-healing dressing as claimed in claim 8, wherein the metal nanoenzyme is an enzyme formed by a simple metal of Au, Ag, Pt, Pd, Rh, Ru, Fe, Co, Ni, Cu or Mn; the nonmetal nanoenzyme is carbide, nitride, phosphide, boride or carbon quantum dot nanoenzyme.
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