CN114470310B - Self-adhesive hydrogel based on tetraase activity nanoenzyme, and preparation method and application thereof - Google Patents
Self-adhesive hydrogel based on tetraase activity nanoenzyme, and preparation method and application thereof Download PDFInfo
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- A61L26/0009—Chemical aspects of, or use of materials for, wound dressings or bandages in liquid, gel or powder form containing macromolecular materials
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- A61L26/00—Chemical aspects of, or use of materials for, wound dressings or bandages in liquid, gel or powder form
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- A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
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- A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
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Abstract
The invention discloses a self-adhesive hydrogel based on a tetraase activity nanoenzyme, a preparation method and application thereof, wherein a hydrogel monomer and a cross-linking agent are uniformly mixed to obtain a dispersion liquid I; adding nano enzyme into the dispersion liquid I to obtain a dispersion liquid II; adding an initiator into the dispersion liquid II to obtain a mixed solution III; pouring the mixed solution III into a hydrogel forming die, standing at room temperature for forming, and cleaning the surface with deionized water to obtain the self-adhesive hydrogel based on the tetraase activity nanoenzyme; and (3) pasting a layer of non-woven fabric or semi-permeable membrane on the outer surface of the hydrogel to obtain the self-adhesive hydrogel dressing based on the tetraase activity nano enzyme. According to the invention, through the compounding of the nano enzyme and the hydrogel, the hydrogel has high-efficiency bacteriostasis and better anti-infection capability, and the wound healing time is obviously shortened.
Description
Technical Field
The invention discloses a self-adhesive hydrogel based on a tetraase activity nanoenzyme, a preparation method and application thereof, and relates to the technical fields of nano catalysis technology, broad-spectrum antibacterial technology and hydrogel dressing preparation.
Background
With the emergence of multidrug resistant microorganisms, antibacterial biomaterials play a key role in effectively inhibiting bacterial infections in public health and biomedical technology. In this regard, antimicrobial hydrogels have been considered as excellent alternatives to traditional solutions. In medical treatment, skin/tissue wounds are prone to serious bacterial infections if not handled properly due to the specific and complex microenvironment of the wound, especially since healing times for certain chronic wounds are typically as long as 1-2 weeks or even longer, and the dressings required to heal the wounds require frequent replacement, resulting in waste of resources. Therefore, the development of multifunctional dressings that have self-adhesion and high-efficiency broad-spectrum antibacterial properties and can accelerate wound repair is a problem to be solved.
In recent years, the nano enzyme has a good application prospect in solving the problem of bacterial drug resistance. In a complex wound environment, nanoenzymes having a single enzyme-like activity exhibit poor antibacterial effects and wound healing effects (oxidase-like activity, peroxidase-like activity, catalase-like activity, and superoxide dismutase-like activity). Therefore, it is urgent to prepare nanoenzymes having various enzyme activities in one body.
Mussel inspired hydrogels are considered a promising wound dressing alternative due to their soft properties similar to the extracellular matrix, available moist environment, regulated physical/chemical properties and excellent tissue adhesion and biocompatibility. CN 113265021A discloses a preparation method and application of an iron-based nanoenzyme hydrogel, which is prepared by an in-situ free radical polymerization method, has peroxidase-like activity and is used in H 2 O 2 When present, the macroporosity and electropositivity of the material can capture and confine bacteria within the destruction range of hydroxyl radicals, immobilize the hydroxyl radicals, and ultimately kill the bacteria. However, the material only has single enzyme-like activity (peroxidase-like enzyme), has poor adhesion, needs to be replaced frequently in the use process, can only play a limited bactericidal effect, and cannot achieve long-term sterilization. Lu et al (Mussel-induced negative and self-setting hydrogel for additive and antibacterial bioelectronics [ J)]Bioactive Materials,2021,6,2676-2687.) a TA-Ag nanoenzyme was prepared by in situ reduction of Ag nanoparticles using Tannic Acid (TA). Then the nanoenzyme is used to prepare the conductive, antibacterial and adhesive hydrogel without external stimulation. Researchers have only used one metal nanoenzyme (Ag nanoparticles). Although the nano enzyme endows hydrogel with antibacterial activity through the synergistic effect of active oxygen species generated by POD-like catalytic reaction and the inherent bactericidal activity of silver, wound healing relates to antibacterial, antioxidant and repair processes, and the rapid healing of wounds cannot be met only by single antibacterial performance. In the patent scheme, nano enzyme with various enzyme activities is compounded with self-adhesive hydrogelIn the healing process of chronic wounds, the nano enzyme generates active oxygen in the micro-acid hydrogel for antibiosis in the antibacterial stage, eliminates over-expressed free radicals in the neutral hydrogel in the antioxidant stage so as to avoid oxidative stress, and utilizes the oxygen generated in the antioxidant stage to promote the reconstruction of new blood vessels and connective tissues in the repair stage and is also necessary for resisting infection. In addition, the hydrogel provides a humid environment for the environment, so that the collagen deposition and angiogenesis are promoted together, and the skin reconstruction is accelerated remarkably.
In conclusion, the nano enzyme with various enzyme activities and the self-adhesive hydrogel are compounded together for healing the chronic wound, so that the nano enzyme can show remarkable antibacterial performance, has excellent capability of scavenging free radicals and provides rich O for wound healing 2 And a moist environment, thereby promoting collagen deposition and angiogenesis significantly accelerating skin remodeling.
Disclosure of Invention
The invention overcomes the defects of the prior art, and aims to solve the technical problem of providing the self-adhesive hydrogel based on the four-enzyme activity nano enzyme, and the preparation method and the application thereof.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
the preparation method of the self-adhesive hydrogel based on the four-enzyme activity nano enzyme comprises the following steps:
step 1) uniformly mixing a proper amount of hydrogel monomer solution and cross-linking agent aqueous solution to obtain dispersion I;
step 2) adding nano enzyme with a certain concentration into the dispersion liquid I, and uniformly mixing to obtain a dispersion liquid II;
step 3) adding an initiator into the dispersion liquid II, and uniformly mixing to obtain a mixed solution III;
step 4) pouring the mixed solution III into a hydrogel forming mold, standing at room temperature for 1-30min, and cleaning the surface with deionized water after forming to obtain the self-adhesive hydrogel based on the tetraase activity nanoenzyme;
and 5) pasting a layer of non-woven fabric or semi-permeable membrane on the outer surface of the hydrogel to obtain the self-adhesive hydrogel dressing based on the tetraase activity nano enzyme.
The mass concentration and dosage ratio of the hydrogel monomer, the cross-linking agent, the nano enzyme and the initiator is as follows: 10-20:1:2-20:2-20.
In the steps 1) to 3), the mixture is uniformly mixed by adopting a magnetic stirring mode, and the speed of the magnetic stirring is 200-600rpm.
Furthermore, in the mixed solution III, the concentration of the hydrogel monomer is 0.1-1g/mL, the concentration of the cross-linking agent is 0.005-0.05g/mL, the content of the nano enzyme is 0.01-1g/mL, and the concentration of the initiator is 0.01-0.1g/mL.
Further, the hydrogel monomer comprises at least one of acrylic acid, acrylamide, N-isopropylacrylamide, tannic acid, tea polyphenol, dopamine and methacrylamide;
further, the cross-linking agent comprises at least one of N, N' -methylene bisacrylamide, double-bonded eugenol, nano clay and tetramethyl ethylene diamine.
Further, the nanoenzyme is an enzyme-like enzyme capable of generating Reactive Oxygen Species (ROS). The enzyme-like enzyme capable of generating active oxygen species comprises at least one of metal nanoenzyme, metal oxide nanoenzyme, nonmetal nanoenzyme, hybrid nanoenzyme or monatin enzyme-like oxidase, peroxidase, catalase or superoxide dismutase.
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.
Further, the concentration of the initiator aqueous solution is 0.01-0.1g/mL; the initiator comprises at least one of ammonium persulfate, ketoglutaric acid, potassium persulfate and polyethylene glycol diacrylate.
The self-adhesive hydrogel based on the four-enzyme active nano enzyme is prepared by the method.
And (3) sticking a layer of non-woven fabric or semi-permeable membrane on the outer surface of the self-adhesive hydrogel based on the four-enzyme activity nano enzyme to prepare the self-adhesive hydrogel dressing based on the four-enzyme activity nano enzyme. The non-woven fabric, the semi-permeable membrane and the like have certain air permeability and can prevent external bacteria from entering the hydrogel fabric or the film, and the self-adhesive hydrogel dressing based on the four-enzyme activity nano enzyme is prepared.
The self-adhesive hydrogel dressing based on the four-enzyme activity nano enzyme is a hydrogel dressing integrating double effects of resisting bacterial infection and accelerating repair. The antibacterial property is broad-spectrum antibacterial and does not generate drug resistance.
The application range of the self-adhesive hydrogel dressing based on the tetrapeptidase activity nano enzyme comprises but is not limited to burn, knife wound, diabetic foot, chronic wound and the like.
Compared with the prior art, the invention has the following beneficial effects:
(1) The self-adhesive hydrogel dressing based on the four-enzyme-activity nano-enzyme provided by the invention shows different enzyme-like activities in different wound environments (for example, in an acidic environment, the peroxidase-like enzyme can react with hydrogen peroxide (H) 2 O 2 ) Converted into hydroxyl free radical (. OH) to play the role of antibiosis; the oxidase-like enzyme can convert oxygen into H 2 O 2 Supplementing certain amount of H for antibacterial stage 2 O 2 (ii) a The neutral or basic environment may be to react H 2 O 2 Or O 2 ·- Conversion to O 2 Providing necessary oxygen for the wound repair stage), thereby achieving the purposes of high-efficiency broad-spectrum sterilization, anti-inflammation and tissue repair.
(2) The self-adhesive hydrogel dressing based on the tetraase activity nanoenzyme prepared by the invention realizes long-term adhesion by dynamically controlling the redox balance among the phenolic quinone groups, achieves the aim of repeated use, effectively fixes bacteria at wounds, prevents the invasion of the bacteria and prevents the waste of dressing resources. 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 nano-enzyme adopted in the mussel-like hydrogel dressing prepared by the invention contains a plurality of metal nano-enzymes with different particle sizes, and active oxygen species can be continuously provided under the action of the nano-enzyme by regularly spraying a low-concentration hydrogen peroxide solution on the wound, so that the healing of the wound is effectively promoted.
(4) 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 is a HRTEM image and an EDS mapping image of Mn-based nanoenzymes prepared in example 1 of the present invention.
FIG. 2 is a diagram showing the ROS activity of Mn-based nanoenzymes prepared in example 1 of the present invention.
FIG. 3 is a diagram showing POD-like activity of carbon-based nanoenzymes prepared in example 5 of the present invention.
FIG. 4 is a graph of in vitro antibacterial performance of Mn-based nanoenzyme prepared in example 1 of the present invention.
FIG. 5 is a graph of in vitro antibacterial performance of Mn-based nanoenzyme hydrogel prepared in example 1 of the present invention.
Detailed Description
The invention will be further explained with reference to the drawings.
1. The preparation method of the self-adhesive hydrogel based on the four-enzyme activity nano-enzyme takes the metal nano-enzyme self-adhesive hydrogel as an example, and the metal nano-enzyme can generate active oxygen species.
The preparation of the metal nano enzyme is implemented by calcining a nano enzyme precursor polymer and a metal compound, wherein the ratio of the precursor polymer to the metal compound is as follows: 0.5-5:1, obtaining the metal nano enzyme. The metal nano enzyme can be formed by Au, ag, pt, pd, rh, ru, fe, co, ni, cu or Mn metal simple substance.
The preparation method of the self-adhesive hydrogel based on the metal nanoenzyme comprises the following steps:
step 1) uniformly mixing a proper amount of hydrogel monomer solution and cross-linking agent aqueous solution to obtain dispersion I;
step 2) adding metal nano enzyme with a certain concentration into the dispersion liquid I, and uniformly mixing to obtain a dispersion liquid II;
step 3) adding an initiator into the dispersion liquid II, and uniformly mixing to obtain a mixed solution III;
step 4) pouring the mixed solution III into a hydrogel forming die, standing for 1-30min at room temperature, and cleaning the surface with deionized water after forming to obtain the self-adhesive hydrogel based on the tetraase activity nanoenzyme;
and 5) pasting a layer of non-woven fabric or semi-permeable membrane on the outer surface of the hydrogel to obtain the self-adhesive hydrogel dressing based on the nano enzyme with the quadruple enzyme activity.
The mass concentration and dosage ratio of the hydrogel monomer, the cross-linking agent, the nano enzyme and the initiator is as follows: 10-20:1:2-20:2-20.
Taking Mn-based nano-enzyme self-adhesive hydrogel as an example, the preparation method comprises the following steps:
preparation of precursor polymer: dissolving and uniformly stirring the triton, the aniline and the pyrrole, and reacting with an initiator (the initiator is ammonium persulfate, ketoglutaric acid, potassium persulfate or polyethylene glycol diacrylate) at a low temperature of 0-3 ℃ to obtain the triton. The mass ratio of the triton to the aniline to the pyrrole to the initiator is as follows: 5-10:30-50:20-30:150-200.
Preparation of Mn-based nanoenzyme: calcining the precursor polymer at 800-1200 ℃ and then mixing with MnCl 2 ·4H 2 And O is uniformly mixed and stirred for 1-3h, centrifugally washed, dried overnight and then calcined for 1-3h at the high temperature of 800-1200 ℃, thus finally obtaining the Mn-based nano enzyme. Precursor polymer and MnCl 2 ·4H 2 The mass ratio of O is 0.5-5:1.
preparation of Mn-based nanoenzyme hydrogel: sequentially adding acrylic acid and an N, N' -methylene bisacrylamide aqueous solution into a reactor, and stirring until the mixture is completely uniform to obtain a dispersion solution I; adding the prepared Mn-based nano enzyme dispersion liquid into the dispersion liquid I, and continuously stirring until the dispersion liquid I is uniformly dispersed to obtain a dispersion liquid II; adding an ammonium persulfate aqueous solution and deionized water into the dispersion liquid II, and stirring until the mixture is completely uniform to obtain a mixed solution III; and pouring the mixed solution III into a hydrogel forming die, standing at room temperature, and after hydrogel is formed, cleaning the surface with deionized water to obtain the self-adhesive Mn-based nanoenzyme hydrogel based on the tetraase activity nanoenzyme. In the step: the mass concentration ratio of the acrylic acid, the N, N' -methylene bisacrylamide, the nano enzyme and the ammonium persulfate is as follows: 10-20:1:2-20:2-20.
Example 1
(1) Preparation of Mn-based nanoenzyme and ROS activity test
Weighing 0.06g of triton, adding the triton into water, performing ultrasonic dissolution, then adding 0.38mL of aniline and 0.29mL of pyrrole, uniformly stirring, then placing into an ice box, then adding precooled 1.825g of ammonium persulfate, standing for reaction for 12h, washing with water, and drying to obtain a precursor polymer. Calcining the polymer at the high temperature of 1000 ℃ and mixing with MnCl with the same mass 2 ·4H 2 And O is uniformly mixed and stirred for 2h, centrifugally washed, dried overnight and then calcined for 2h at the high temperature of 1000 ℃, and finally the Mn-based nanoenzyme is obtained and is marked as C-Mn.
(2) Preparation of self-adhesive Mn-based nanoenzyme hydrogel based on tetraase activity nanoenzyme
Sequentially adding 3mL of acrylic acid and 0.5mL of N, N' -methylene bisacrylamide aqueous solution (the concentration is 0.01 g/mL) into a reactor, and magnetically stirring for 3min until the mixture is completely uniform to obtain a dispersion solution I; adding 0.2mL of Mn-based nanoenzyme dispersion (with the concentration of 0.022 g/mL) prepared in the step (1) of the embodiment into the dispersion I, and continuing to stir by magnetic force until the dispersion is uniform, so as to obtain a dispersion II; adding 1.3mL of ammonium persulfate aqueous solution (with the concentration of 0.02 g/mL) and 5mL of deionized water into the dispersion liquid II, and magnetically stirring until the mixture is completely uniform to obtain a mixed solution III; and pouring the mixed solution III into a hydrogel forming die, and standing for 20min at room temperature. And after the hydrogel is formed, cleaning the surface of the hydrogel by using deionized water to obtain the self-adhesive Mn-based nanoenzyme hydrogel based on the tetraase activity nanoenzyme.
(3) ROS activity test of Mn-based nanoenzyme
FIG. 1 shows HRTEM image (high resolution transmission electron micrograph, FIG. A) and EDS mapping image (energy distribution surface scanning analysis, FIG. B) of the prepared Mn-based nanoenzyme. As can be seen from FIG. 1, the Mn-based hollow spherical nanoenzyme is successfully prepared, and the diameter is about 100 nm. In the EDS mapping chart of the graph B, the upper right graph is a carbon C distribution chart, the lower left graph is a nitrogen N distribution chart, the lower right graph is a manganese Mn distribution chart, the upper left graph is a comprehensive distribution chart of three elements, and Mn can be seen to be uniformly dispersed on the surface of the nano-enzyme in the EDS mapping chart.
And testing the ROS activity of the prepared Mn-based nanoenzyme by using a portable dissolved oxygen tester and an ultraviolet-visible spectrophotometer. FIG. 2 shows the ROS activity patterns of the Mn-based nanoenzymes prepared (A is an oxidase-like enzyme activity pattern (OXD), B is a peroxidase-like enzyme activity Pattern (POD), C is a catalase-like enzyme activity pattern (CAT), and D is a superoxide dismutase-like enzyme activity pattern (SOD)). FIG. 2 is a graph A showing the results of measurement of dissolved oxygen in Mn-based oxidases, showing the trend of the concentration of oxygen content with the lapse of time; b is an ultraviolet-visible spectrum of Mn-based peroxidase, C is an ultraviolet-visible spectrum of Mn-based catalase, and the graph shows the trend that the absorbance intensity changes along with different PH values and time at the wavelength of 652 nm; the absorbance intensity of Mn-based superoxide dismutase is shown in the D-diagram. As can be seen from FIG. 2, the prepared Mn-based nanoenzyme has four enzyme activities and can be used as an enzyme for generating active oxygen.
(4) In vitro antibacterial experiment of Mn-based nanoenzyme
The antibacterial performance of the Mn-based nanoenzyme is tested by adopting a flat plate counting method. Gram-negative bacteria (escherichia coli, e.coli), gram-positive bacteria (staphylococcus aureus, s.aureus) were treated differently with Mn-based nanoenzymes, respectively: NIR (+) H 2 O 2 (+)，NIR(+)H 2 O 2 (-)，NIR(-)H 2 O 2 (+) and NIR (-) H 2 O 2 (-). Mn-based nanoenzyme solutions with different concentrations and 100 mu L of bacterial solution are mixed in a 96-well plate, and the final Mn-based nanoenzyme concentration is (0, 25, 50, 100, 200) mu g/mL respectively. The total volume of the solution in each well was 200. Mu.L, and the final concentration of hydrogen peroxide was 200. Mu.M. After 1 hour incubation, NIR (+) H 2 O 2 (+) and NIR (+) H 2 O 2 The (-) group was further irradiated with a 1064nm laser (1W/cm) 2 ) Irradiating for 5min. The incubation of each group was then continued for 2h at 37 ℃. Diluting the bacterial solution and taking 10After 0. Mu.l of the suspension was applied to LB agar and incubated at 37 ℃ for 24 hours, plate colonies were counted and the antibacterial efficiency was evaluated. FIG. 4 is a data diagram of in vitro antibacterial experiments of the prepared Mn-based nanoenzyme. A is a graph of the sterilization performance of Mn-based nanoenzyme on escherichia coli, the abscissa is the concentration of the nanoenzyme, and the ordinate is the survival rate of bacteria; and the B picture is a graph of the bactericidal performance of Mn-based nanoenzyme on staphylococcus aureus, the abscissa is the concentration of the nanoenzyme, and the ordinate is the survival rate of bacteria. As can be seen from FIG. 4, the Mn-based nanoenzyme has a high bactericidal effect on Escherichia coli and Staphylococcus aureus, and also has photothermal properties.
(5) In-vitro antibacterial experiment of self-adhesive Mn-based nanoenzyme hydrogel based on four-enzyme active nanoenzyme
Using a wafer diffusion method (Rota, carramine, burillo,&herrera, 2004) demonstrated antimicrobial activity of the reusable self-adhesive Mn-based nanoenzyme hydrogel against escherichia coli (e.coil), staphylococcus aureus (s.aureus), and methicillin-resistant staphylococcus aureus (MRSA). Nutrient agar was first sterilized in an autoclave and cooled to 45-50 ℃ and then poured into 90mm petri dishes and 100mL of fresh inoculum suspension (cells in logarithmic growth phase) was spread overnight. After curing, mn-based nanoenzyme hydrogel samples (6 mm in diameter) were transferred to Petri dishes. Likewise, hydrogels without Mn-based nanoenzymes served as blank controls. The inoculated discs were incubated at 37 ℃ for 24h. The antimicrobial activity of the hydrogels was evaluated by the diameter of the inhibition zone (DIZ) surrounding the sample, including the hydrogel diameter, as measured by digital calipers (Akin, aktumsek,&nosro, 2010) and recorded in millimeters to evaluate antimicrobial activity between samples. All experiments were performed in triplicate. FIG. 5 is a data diagram of in vitro antibacterial experiments of the prepared Mn-based nanoenzyme hydrogel. From the comparison result in FIG. 5, it can be concluded that the prepared Mn-based nanoenzyme hydrogel is in H 2 O 2 The sterilization efficiency of the nano enzyme on the escherichia coli under the existing condition is about 50%, which shows that the nano enzyme plays a crucial role in the hydrogel antibacterial process.
Example 2
(1) 0.05g of triton is weighed and added into water for ultrasonic dissolution, and then 0.20mL of aniline and water are added0.20mL of pyrrole, uniformly stirring, placing into an ice box, adding precooled 1.50g of ammonium persulfate, standing for reacting for 8 hours, washing with water and drying to obtain a precursor polymer. Calcining the precursor polymer at 800 ℃ and then mixing with MnCl 2 ·4H 2 And O is uniformly mixed and stirred for 1h, centrifugally washed, dried overnight and then calcined for 1-3h at the high temperature of 800 ℃ to finally obtain the Mn-based nanoenzyme. Precursor polymer and MnCl 2 ·4H 2 The mass ratio of O is 0.5:1.
(2) Preparation of self-adhesive Mn-based nano enzyme hydrogel based on four-enzyme active nano enzyme
Sequentially adding acrylic acid and an N, N' -methylene bisacrylamide aqueous solution (the concentration is 0.01 g/mL) into a reactor, and magnetically stirring for 2min till the mixture is completely uniform to obtain a dispersion solution I; adding the Mn-based nanoenzyme dispersion (with the concentration of 0.022 g/mL) prepared in the step (1) of the embodiment into the dispersion I, and continuing to magnetically stir until the Mn-based nanoenzyme dispersion is uniformly dispersed to obtain a dispersion II; adding an ammonium persulfate aqueous solution (with the concentration of 0.02 g/mL) and 5mL of deionized water into the dispersion liquid II, and magnetically stirring until the mixture is completely uniform to obtain a mixed solution III; and pouring the mixed solution III into a hydrogel forming mold, and standing at room temperature for 30min. And after the hydrogel is formed, cleaning the surface of the hydrogel by using deionized water to obtain the self-adhesive Mn-based nanoenzyme hydrogel based on the tetraase activity nanoenzyme.
The mass concentration ratio of the acrylic acid, the N, N' -methylene bisacrylamide, the nano enzyme and the ammonium persulfate is as follows: 10:1:2:2.
Example 3
(1) Weighing 0.10g of triton, adding the triton into water, performing ultrasonic dissolution, then adding 0.50mL of aniline and 0.30mL of pyrrole, uniformly stirring, then placing into an ice box, then adding pre-cooled 2.00g of ammonium persulfate, standing for reaction for 12h, washing with water, and drying to obtain a precursor polymer. Calcining the precursor polymer at high temperature of 1200 ℃ and then mixing with MnCl 2 ·4H 2 And O is uniformly mixed and stirred for 3h, centrifugally washed, dried overnight and then calcined for 1-3h at the high temperature of 800 ℃ to finally obtain the Mn-based nanoenzyme. Precursor polymer and MnCl 2 ·4H 2 The mass ratio of O is 0.5:1.
(2) Preparation of self-adhesive Mn-based nanoenzyme hydrogel based on tetraase activity nanoenzyme
Sequentially adding acrylic acid and an N, N '-methylene-bisacrylamide aqueous solution (the concentration is 0.01 g/mL) into a reactor, and magnetically stirring until the acrylic acid and the N, N' -methylene-bisacrylamide aqueous solution are completely uniform to obtain a dispersion solution I; adding the Mn-based nanoenzyme dispersion (with the concentration of 0.022 g/mL) prepared in the step (1) of the embodiment into the dispersion I, and continuing to magnetically stir until the Mn-based nanoenzyme dispersion is uniformly dispersed to obtain a dispersion II; adding an ammonium persulfate aqueous solution (with the concentration of 0.02 g/mL) and 5mL of deionized water into the dispersion liquid II, and magnetically stirring until the mixture is completely uniform to obtain a mixed solution III; and pouring the mixed solution III into a hydrogel forming mold, and standing at room temperature for 30min. And after the hydrogel is formed, cleaning the surface of the hydrogel by using deionized water to obtain the self-adhesive Mn-based nanoenzyme hydrogel based on the tetraase activity nanoenzyme.
The mass concentration ratio of the acrylic acid, the N, N' -methylene bisacrylamide, the nano enzyme and the ammonium persulfate is as follows: 20:1:20:20.
Example 4
(1) Weighing 0.08g of triton, adding the triton into water, performing ultrasonic dissolution, then adding 0.40mL of aniline and 0.25mL of pyrrole, uniformly stirring, then placing into an ice box, then adding precooled 1.50g of ammonium persulfate, standing for reaction for 10h, and washing and drying to obtain a precursor polymer. Calcining the precursor polymer at the high temperature of 1100 ℃ and then mixing with MnCl 2 ·4H 2 And O is uniformly mixed and stirred for 4 hours, centrifugally washed, dried overnight and then calcined for 3 hours at the high temperature of 1100 ℃, thus finally obtaining the Mn-based nanoenzyme. Precursor polymer and MnCl 2 ·4H 2 The mass ratio of O is 5:1.
(2) Preparation of self-adhesive Mn-based nanoenzyme hydrogel based on tetraase activity nanoenzyme
Sequentially adding acrylic acid and an N, N' -methylene bisacrylamide aqueous solution (the concentration is 0.01 g/mL) into a reactor, and magnetically stirring until the mixture is completely uniform to obtain a dispersion solution I; adding the Mn-based nanoenzyme dispersion (with the concentration of 0.022 g/mL) prepared in the step (1) of the embodiment into the dispersion I, and continuing to magnetically stir until the Mn-based nanoenzyme dispersion is uniformly dispersed to obtain a dispersion II; adding an ammonium persulfate aqueous solution (with the concentration of 0.02 g/mL) and 5mL of deionized water into the dispersion liquid II, and magnetically stirring until the mixture is completely uniform to obtain a mixed solution III; and pouring the mixed solution III into a hydrogel forming die, and standing for 30min at room temperature. And after the hydrogel is formed, cleaning the surface of the hydrogel by using deionized water to obtain the self-adhesive Mn-based nanoenzyme hydrogel based on the tetraase activity nanoenzyme.
The mass concentration ratio of the acrylic acid, the N, N' -methylene bisacrylamide, the nano enzyme and the ammonium persulfate is as follows: 10:1:10:5.
2. The invention relates to a preparation method of self-adhesive hydrogel based on four-enzyme active nano-enzyme, which takes non-metal nano-enzyme self-adhesive hydrogel as an example, and the non-metal nano-enzyme can generate active oxygen species.
The preparation of the nonmetal nano enzyme is realized by calcining a nano enzyme precursor polymer and a nonmetal compound, wherein the ratio of the precursor polymer to the nonmetal compound is as follows: 0.5-5:1, obtaining the nonmetal nano enzyme. The non-metal nano enzyme can be carbide, nitride, phosphide, boride or carbon quantum dot nano enzyme.
The preparation method of the self-adhesive hydrogel based on the nonmetal nano-enzyme comprises the following steps:
step 1) uniformly mixing a proper amount of hydrogel monomer solution and cross-linking agent aqueous solution to obtain dispersion I;
step 2) adding nonmetallic nano enzyme with a certain concentration into the dispersion liquid I, and uniformly mixing to obtain a dispersion liquid II;
step 3) adding an initiator into the dispersion liquid II, and uniformly mixing to obtain a mixed solution III;
step 4) pouring the mixed solution III into a hydrogel forming die, standing for 1-30min at room temperature, and cleaning the surface with deionized water after forming to obtain the self-adhesive hydrogel based on the tetraase activity nanoenzyme;
and 5) pasting a layer of non-woven fabric or semi-permeable membrane on the outer surface of the hydrogel to obtain the self-adhesive hydrogel dressing based on the tetraase activity nano enzyme.
The mass concentration and dosage ratio of the hydrogel monomer, the cross-linking agent, the nano enzyme and the initiator is as follows: 10-20:1:2-20:2-20.
Taking the carbon-based nano enzyme self-adhesive hydrogel as an example, the preparation method comprises the following steps:
preparation of precursor polymer: dissolving and uniformly stirring the triton, the aniline and the pyrrole, and reacting with an initiator (the initiator is ammonium persulfate, ketoglutaric acid, potassium persulfate or polyethylene glycol diacrylate) at a low temperature of 0-3 ℃ to obtain the triton. The mass ratio of triton, aniline, pyrrole and initiator is as follows: 5-10:30-50:20-30:150-200.
Preparing carbon-based nano enzyme: and (3) calcining the precursor polymer at different carbonization temperatures for 1-3h to finally obtain the carbon-based nano enzyme at different temperatures.
Preparing carbon-based nano enzyme hydrogel: sequentially adding acrylic acid and an N, N' -methylene bisacrylamide aqueous solution into a reactor, and stirring until the mixture is completely uniform to obtain a dispersion solution I; adding the prepared carbon-based nano enzyme dispersion liquid into the dispersion liquid I, and continuously stirring until the dispersion liquid is uniformly dispersed to obtain a dispersion liquid II; adding an ammonium sulfite aqueous solution and deionized water into the dispersion liquid II, and stirring until the mixture is completely uniform to obtain a mixed solution III; and pouring the mixed solution III into a hydrogel forming mold, standing at room temperature, and after hydrogel is formed, cleaning the surface of the hydrogel with deionized water to obtain the self-adhesive carbon-based nano enzyme hydrogel based on the tetrapase activity nano enzyme. In this step: the mass concentration ratio of the acrylic acid, the N, N' -methylene bisacrylamide, the nano enzyme and the ammonium sulfite is as follows: 10-20:1:2-20:2-20.
Example 5
Preparation of carbon-based nanoenzyme at different temperatures
Weighing 0.06g of triton, adding the triton into water, performing ultrasonic dissolution, then adding 0.38mL of aniline and 0.29mL of pyrrole, uniformly stirring, then placing into an ice box, then adding precooled 1.825g of ammonium persulfate, standing for reaction for 12h, washing with water, and drying to obtain a precursor polymer. And then, carrying out high-temperature calcination for 2h at different carbonization temperatures (200, 400, 800 and 1000 ℃) to finally obtain carbon-based nano enzyme samples at different temperatures, and marking the carbon-based nano enzyme samples as C2, C4, C8 and C12. These carbon-based nanoenzymes were then subjected to catalytic TMB reactions to test their POD-like activity.
FIG. 3 is a graph showing POD-like activity data of the prepared carbon-based nanoenzymes. As can be seen from FIG. 3, the absorbance at 652nm gradually decreased with the increase of the carbonization temperature, which indicates that the activity of the prepared carbohydrase decreased with the increase of the carbonization temperature, wherein the most excellent property was C2.
Preparation of self-adhesive carbon-based nano enzyme hydrogel
Sequentially adding 3.5mL of acrylic acid and 0.8mL of N, N' -methylene bisacrylamide aqueous solution into a reactor, and magnetically stirring for 4min until the mixture is completely uniform to obtain a dispersion solution I; adding 0.5mL of prepared carbon-based nano enzyme dispersion liquid into the dispersion liquid I, and continuing to stir by magnetic force until the dispersion liquid is uniformly dispersed to obtain a dispersion liquid II; adding 2.2mL of ammonium sulfite aqueous solution and 3mL of deionized water into the dispersion liquid II, and magnetically stirring until the mixture is completely uniform to obtain a mixed solution III; and pouring the mixed solution III into a hydrogel forming die, and standing for 15min at room temperature. And after the hydrogel is formed, cleaning the surface with deionized water to obtain the self-adhesive carbon-based nano enzyme hydrogel.
Example 6
Preparation of carbon-based nanoenzyme at different temperatures
Weighing 0.02g of triton, adding the triton into water, performing ultrasonic dissolution, then adding 0.30mL of aniline and 0.20mL of pyrrole, uniformly stirring, then placing into an ice box, then adding precooled 1.0g of ammonium persulfate, standing for reaction for 12h, and washing and drying to obtain a precursor polymer. Then, high-temperature calcination is carried out for 2 hours at different carbonization temperatures (200, 400, 800 and 1000 ℃) to finally obtain carbon-based nano enzyme samples at different temperatures.
Example 7
Preparation of carbon-based nanoenzyme at different temperatures
Weighing 0.1g of triton, adding the triton into water, performing ultrasonic dissolution, then adding 0.50mL of aniline and 0.50mL of pyrrole, uniformly stirring, then placing into an ice box, then adding pre-cooled 2.0g of ammonium persulfate, standing for reaction for 10h, washing with water, and drying to obtain a precursor polymer. Then, high-temperature calcination is carried out for 3 hours at different carbonization temperatures (200, 400, 800 and 1000 ℃) to finally obtain carbon-based nano enzyme samples at different temperatures.
The self-adhesive hydrogel and dressing based on the nano-enzyme with the tetrapanase activity, provided by the invention, contain nano-enzyme which plays a role in catalyzing decomposition of hydrogen peroxide in the antibacterial and repairing processes and has enzyme-like characteristics, such as peroxidase, catalase, oxidase and the like. After the wound is cleaned, low-concentration hydrogen peroxide is sprayed, and one or more of active oxygen such as high-toxicity hydroxyl free radicals, singlet oxygen, superoxide anions and the like are generated by catalyzing the hydrogen peroxide through the nano enzyme, so that high-efficiency sterilization is realized, and the nano enzyme is rich in types; can also catalyze the generation of oxygen, which is important for the reconstruction of new blood vessels and connective tissues and the construction of infectious capacity and is critical for the treatment of wounds which are difficult to heal. The hydrogel dressing has mild preparation conditions and simple and convenient operation, achieves the purpose of repeated use through repeated self-adhesion, and achieves the purpose of long-acting antibiosis through regularly spraying hydrogen peroxide; the hydrogel can keep the local moisture of the wound, accelerate the healing of the wound and absorb a small amount of seepage.
The self-adhesive hydrogel based on the four-enzyme activity nano enzyme can maintain the chemical balance of the phenolic quinone by utilizing a limited space and electron transfer, thereby realizing the self-adhesion of the mussel and the repeated adhesion with the skin, achieving the repeated utilization of the dressing, and spraying hydrogen peroxide again at a certain interval to achieve the purpose of long-acting antibiosis; the hydrogel can keep the local moisture of the wound, accelerate the healing of the wound and absorb a small amount of seepage.
The hydrogel disclosed by the invention does not need to use extra glue, so that allergy caused by long-term adhesion of local skin is avoided, and the economic cost of a patient is reduced by utilizing the characteristic of repeated adhesion. The raw materials used in the invention have the advantages of low cost, good biocompatibility and the like, and the hydrogel dressing has the advantages of simple process, short production period, no toxic substances and easy batch production.
It should be 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.
The embodiments of the present invention have been described in detail with reference to the accompanying drawings, but the present invention is not limited to the above embodiments, and various changes can be made within the knowledge of those skilled in the art without departing from the gist of the present invention.
Claims (7)
1. The preparation method of the self-adhesive hydrogel based on the four-enzyme activity nano enzyme is characterized by comprising the following steps:
step 1) uniformly mixing a hydrogel monomer solution and a cross-linking agent aqueous solution to obtain a dispersion solution I;
step 2) adding nano enzyme into the dispersion liquid I, and uniformly mixing to obtain a dispersion liquid II;
step 3) adding an initiator into the dispersion liquid II, and uniformly mixing to obtain a mixed solution III;
step 4), standing and forming the mixed solution III, and cleaning the surface to obtain the self-adhesive hydrogel based on the tetraase activity nanoenzyme;
the mass concentration ratio of the hydrogel monomer, the cross-linking agent, the nano enzyme and the initiator is as follows: 10-20;
in the mixed solution III, the concentration of a hydrogel monomer is 0.1-1g/mL, the concentration of a cross-linking agent is 0.005-0.05g/mL, the content of nano enzyme is 0.01-1g/mL, and the concentration of an initiator is 0.01-0.1g/mL;
the nano enzyme is an enzyme capable of generating active oxygen species, and specifically comprises at least one of metal nano enzyme, metal oxide nano enzyme, nonmetal nano enzyme, hybrid nano enzyme or monatomic enzyme, such as oxidase, peroxidase, catalase or superoxide dismutase.
2. The method for preparing the self-adhesive hydrogel based on the tetraase-active nanoenzyme according to claim 1, wherein the hydrogel monomer comprises at least one of acrylic acid, acrylamide, N-isopropylacrylamide, dopamine and methacrylamide; the cross-linking agent comprises at least one of N, N' -methylene bisacrylamide, double-bonded eugenol and tetramethyl ethylenediamine.
3. The method for preparing the self-adhesive hydrogel based on the tetraase-activity nanoenzyme according to claim 1, 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.
4. The method for preparing the self-adhesive hydrogel based on the tetraase-activity nanoenzyme according to claim 1, wherein the initiator comprises at least one of ammonium persulfate, ketoglutaric acid, potassium persulfate and polyethylene glycol diacrylate.
5. The self-adhesive hydrogel based on a tetraase-active nanoenzyme prepared by the process according to any one of claims 1 to 4.
6. The self-adhesive hydrogel dressing based on the tetraase activity nanoenzyme, which is prepared by applying a layer of non-woven fabric or semi-permeable membrane on the outer surface of the self-adhesive hydrogel based on the tetraase activity nanoenzyme of claim 5.
7. Use of the tetra-enzyme active nanoenzyme based self-adhesive hydrogel according to claim 6 for the preparation or use as a wound dressing.
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