CN115252886A - Preparation method of autocatalytic injectable hydrogel dressing for treating bacterial infection - Google Patents
Preparation method of autocatalytic injectable hydrogel dressing for treating bacterial infection Download PDFInfo
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Abstract
The invention discloses a preparation method of autocatalysis injectable hydrogel for treating bacterial infection, which can rapidly activate ammonium persulfate to generate hydroxyl free radical to have peroxidase activity and kill bacteria through dynamic oxidation reduction of tannic acid-iron, and can promote polymerization of glycidyl methacrylate modified polylysine. The hydrogel dressing prepared by the method has antibacterial property, anti-inflammatory property, injectability and adhesiveness, can remove excessive ROS, and promotes wound healing of bacterial infection.
Description
Technical Field
The invention belongs to the technical field of dressings, and particularly relates to a preparation method of an autocatalytic injectable hydrogel dressing for treating bacterial infection.
Background
Bacterial infection is the most common problem in wound healing, involuntary movement pain, metabolism and immune system disorder can occur to infected wounds, the life quality of patients is affected, serious patients are even life-threatening, and the bacterial infection can cause inflammation and further affect the wound healing quality.
Currently, many antimicrobial materials, including antibiotics, metals, and carbon nanomaterials (copper oxide, zinc oxide, carbon nanotubes, and graphene) are used for antimicrobial therapy. However, these materials are prone to cause the disadvantages of increased microbial drug resistance, heavy metal poisoning, mismatched drug release, non-biodegradability or insufficient cell compatibility, etc., and are not favorable for clinical application. Photothermal therapy (PTT) is considered as an effective method for killing microorganisms because of its advantages of deep tissue penetration, low cytotoxicity, low tissue damage, etc. However, the existing wound aiming at bacterial infection still cannot meet the requirement of wound surface rapid repair.
Disclosure of Invention
The technical problem to be solved by the present invention is to provide a method for preparing an autocatalytic injectable hydrogel dressing for the treatment of bacterial infection, in view of the above-mentioned deficiencies of the prior art. The preparation method of the autocatalytic injectable hydrogel dressing for treating bacterial infection comprises the steps of adding tannic acid, iron and ammonium persulfate into a polyvinyl alcohol solution containing glycidyl methacrylate modified polylysine, and standing for reaction to prepare the autocatalytic injectable hydrogel dressing, wherein the dynamic redox of TA-Fe can be fully utilized by the dressing to rapidly activate APS generation-OH to kill bacteria.
In order to solve the technical problems, the invention adopts the technical scheme that: a method of preparing an autocatalytic injectable hydrogel dressing for the treatment of bacterial infection comprising: adding tannic acid, iron and ammonium persulfate into a polyvinyl alcohol solution containing glycidyl methacrylate modified polylysine to obtain a dressing preparation solution, and standing the dressing preparation solution at 15-25 ℃ for 1-20 min to obtain the autocatalytic injectable hydrogel dressing for treating bacterial infection; the grafting rate of the glycidyl methacrylate modified polylysine is 40-50%; the dressing preparation liquid contains 0.01-0.04 wt% of tannic acid, 0.3-1.2 wt% of iron and 0.02-0.03 wt% of ammonium persulfate.
The preparation method of the autocatalytic injectable hydrogel dressing for treating bacterial infection is characterized in that the glycidyl methacrylate modified polylysine is prepared by stirring and reacting glycidyl methacrylate and polylysine solution at the temperature of 80-90 ℃ for 5-7 h.
The preparation method of the autocatalytic injectable hydrogel dressing for treating bacterial infection is characterized in that the molar ratio of the glycidyl methacrylate to the polylysine is (1-2): 1.
the preparation method of the autocatalytic injectable hydrogel dressing for treating bacterial infection is characterized in that the molecular weight of the polylysine is 4000.
The preparation method of the autocatalytic injectable hydrogel dressing for treating bacterial infection is characterized in that the polyvinyl alcohol solution containing the glycidyl methacrylate modified polylysine is obtained by adding the glycidyl methacrylate modified polylysine into the polyvinyl alcohol solution, the mass percentage of polyvinyl alcohol in the polyvinyl alcohol solution is 5% -10%, and the mass percentage of glycidyl methacrylate modified polylysine in the polyvinyl alcohol solution containing the glycidyl methacrylate modified polylysine is 10%.
The preparation method of the autocatalytic injectable hydrogel dressing for treating bacterial infection is characterized in that the molecular weight of polyvinyl alcohol in the polyvinyl alcohol solution is 90000.
Compared with the prior art, the invention has the following advantages:
1. the invention provides a preparation method of an autocatalytic injectable hydrogel dressing for treating bacterial infection, which is characterized in that tannic acid, iron and ammonium persulfate are added into a polyvinyl alcohol solution containing glycidyl methacrylate modified polylysine, and the autocatalytic injectable hydrogel dressing is prepared by standing reaction.
2. Preferably, the modified polylysine comprises the polylysine modified by glycidyl methacrylate, and the polylysine can realize in-situ crosslinking after modification, realize room-temperature gelling, and do not need external stimulation such as ultraviolet irradiation or thermal initiation.
3. The hydrogel dressing prepared by the method has adhesiveness and injectability, can resist inflammation, remove excessive ROS and eradicate bacteria, and is convenient for clinical application.
The technical scheme of the invention is further described in detail by combining the accompanying drawings and the embodiment
Drawings
FIG. 1 is a Fourier transform infrared spectrum of the methacrylic acid-modified polylysine prepared in example 1.
Figure 2 is a fourier transform infrared spectrum of the hydrogel dressing prepared in example 1.
Fig. 3 is an XPS plot of the hydrogel dressing prepared in example 1.
Fig. 4 is a scanning electron micrograph of the hydrogel dressing prepared in example 1.
Fig. 5 is a graph of the injectability of the hydrogel dressing prepared in example 1.
Fig. 6 is a graph showing the adhesive properties of the hydrogel dressing prepared in example 1.
Fig. 7 is a graph showing the antibacterial properties of the hydrogel dressing prepared in example 1.
Fig. 8 is a graph of photothermal performance of the hydrogel dressing prepared in example 1.
FIG. 9 is a graph showing peroxidase-like properties of the hydrogel dressing prepared in example 1.
Fig. 10 is a graph showing the oxidation resistance of the hydrogel dressing prepared in example 1.
Detailed Description
Example 1
This example provides a method of preparing an autocatalytic injectable hydrogel dressing for the treatment of bacterial infections, comprising the steps of:
step one, dissolving polyvinyl alcohol (PVA) in water at the temperature of 90 ℃ until the PVA is completely clear to obtain a polyvinyl alcohol solution; in the polyvinyl alcohol solution, the mass percentage of polyvinyl alcohol (PVA) is 5%; the polyvinyl alcohol (PVA) has a number average molecular weight of 90000;
step two, providing the glycidyl methacrylate modified polylysine powder (EPL-GMA), which specifically comprises the following steps:
step 201, dissolving polylysine (EPL) in deionized water to obtain a polylysine solution with the mass percentage of 10%; the polylysine (EPL) has a molecular weight of 4000;
step 202, adding Glycidyl Methacrylate (GMA) into the polylysine solution at the temperature of 80 ℃, and stirring for reaction for 6 hours; the molar ratio of the glycidyl methacrylate to the polylysine is 1:1; the molecular weight of the Glycidyl Methacrylate (GMA) is 142;
step 203, filtering the system reacted in the step 202 by using a dialysis bag for 4 days (the molecular weight cut-off of the dialysis bag is 1000), replacing 3 times per day of dialysis water, and freeze-drying after the dialysis is finished to obtain poly-lysine powder (EPL-GMA) modified by glycidyl methacrylate; the grafting rate of the poly-lysine modified by the glycidyl methacrylate is 40 percent; the grafting rate is calculated by utilizing the relationship between the standard curve of the glycidyl methacrylate under different concentrations and the mass percent of the polylysine powder modified by the glycidyl methacrylate; the freeze-drying may be freeze-drying at-80 ℃ for 3 days;
step three, adding the glycidyl methacrylate modified polylysine powder (EPL-GMA) obtained in the step two into the polyvinyl alcohol solution obtained in the step one, and stirring until the glycidyl methacrylate modified polylysine powder is completely dissolved to obtain a mixed solution I; the mass percentage content of the glycidyl methacrylate modified polylysine (EPL-GMA) in the mixed solution I is 10%;
step four, adding Tannic Acid (TA), iron (Fe) and Ammonium Persulfate (APS) into the mixed solution I obtained in the step three, and stirring to uniformly mix to obtain dressing preparation liquid; in the dressing preparation liquid, the mass percentage of Tannic Acid (TA) is 0.02%, the mass percentage of iron (Fe) is 0.6%, and the mass percentage of Ammonium Persulfate (APS) is 0.02%; the molecular weight of Tannic Acid (TA) is 220, the molecular weight of iron (Fe) is 270, and the molecular weight of Ammonium Persulfate (APS) is 228;
and step five, standing the dressing preparation solution obtained in the step four at 18 ℃ for 5min to obtain the autocatalysis injectable hydrogel dressing (TFAEP) for treating bacterial infection.
Example 2
This example provides a method of preparing an autocatalytic injectable hydrogel dressing for the treatment of bacterial infections, comprising the steps of:
step one, dissolving polyvinyl alcohol (PVA) in water at the temperature of 95 ℃ until the PVA is completely clear to obtain a polyvinyl alcohol solution; in the polyvinyl alcohol solution, the mass percentage of polyvinyl alcohol (PVA) is 6%; the polyvinyl alcohol (PVA) has a number average molecular weight of 90000;
step two, providing the glycidyl methacrylate modified polylysine powder (EPL-GMA), which specifically comprises the following steps:
step 201, dissolving polylysine (EPL) in deionized water to obtain a polylysine solution with the mass percentage of 10%; the polylysine (EPL) has a molecular weight of 4000;
step 202, adding Glycidyl Methacrylate (GMA) into the polylysine solution at 85 ℃, and stirring for reaction for 7 hours; the molar ratio of the glycidyl methacrylate to the polylysine is 1.5:1; the molecular weight of the Glycidyl Methacrylate (GMA) is 142;
step 203, filtering the system reacted in the step 202 by using a dialysis bag for 4 days (the molecular weight cut-off of the dialysis bag is 1000), replacing 3 times per day of dialysis water, and freeze-drying after the dialysis is finished to obtain poly-lysine powder (EPL-GMA) modified by glycidyl methacrylate; the grafting rate of the glycidyl methacrylate modified polylysine is 45 percent; the freeze-drying may be freeze-drying at-80 ℃ for 3 days;
step three, adding the glycidyl methacrylate modified polylysine powder (EPL-GMA) obtained in the step two into the polyvinyl alcohol solution obtained in the step one, and stirring until the glycidyl methacrylate modified polylysine powder is completely dissolved to obtain a mixed solution I; the mass percentage content of the glycidyl methacrylate modified polylysine (EPL-GMA) in the mixed solution I is 10%;
step four, adding Tannic Acid (TA), iron (Fe) and Ammonium Persulfate (APS) into the mixed solution I obtained in the step three, and stirring to uniformly mix to obtain dressing preparation liquid; in the dressing preparation liquid, the mass percentage content of Tannic Acid (TA) is 0.03%, the mass percentage content of iron (Fe) is 0.9%, and the mass percentage content of Ammonium Persulfate (APS) is 0.022%; the molecular weight of Tannic Acid (TA) is 220, the molecular weight of iron (Fe) is 270, and the molecular weight of Ammonium Persulfate (APS) is 228;
and step five, standing the dressing preparation solution obtained in the step four at 20 ℃ for 10min to obtain the autocatalysis injectable hydrogel dressing (TFAEP) for treating bacterial infection.
The hydrogel dressing of this example performed substantially the same as example 1.
Example 3
This example provides a method of preparing an autocatalytic injectable hydrogel dressing for the treatment of bacterial infections, comprising the steps of:
step one, dissolving polyvinyl alcohol (PVA) in water at the temperature of 100 ℃ until the PVA is completely clear to obtain a polyvinyl alcohol solution; in the polyvinyl alcohol solution, the mass percentage of polyvinyl alcohol (PVA) is 7%; the number average molecular weight of the polyvinyl alcohol (PVA) is 100000;
step two, providing the glycidyl methacrylate modified polylysine powder (EPL-GMA), which specifically comprises the following steps:
step 201, dissolving polylysine (EPL) in deionized water to obtain a polylysine solution with the mass percentage of 10%; the polylysine (EPL) has a molecular weight of 4000;
step 202, adding Glycidyl Methacrylate (GMA) into the polylysine solution at 90 ℃, and stirring to react for 5 hours; the molar ratio of the glycidyl methacrylate to the polylysine is 2:1; the molecular weight of the Glycidyl Methacrylate (GMA) is 142;
step 203, filtering the system reacted in the step 202 by using a dialysis bag for 4 days (the molecular weight cut-off of the dialysis bag is 1000), replacing 3 times per day of dialysis water, and freeze-drying after the dialysis is finished to obtain poly-lysine powder (EPL-GMA) modified by glycidyl methacrylate; the grafting rate of the polylysine modified by the glycidyl methacrylate is 50 percent; the freeze-drying may be freeze-drying at-80 ℃ for 3 days;
step three, adding the glycidyl methacrylate modified polylysine powder (EPL-GMA) obtained in the step two into the polyvinyl alcohol solution obtained in the step one, and stirring until the glycidyl methacrylate modified polylysine powder is completely dissolved to obtain a mixed solution I; the mass percentage content of the glycidyl methacrylate modified polylysine (EPL-GMA) in the mixed solution I is 10%;
step four, adding Tannic Acid (TA), iron (Fe) and Ammonium Persulfate (APS) into the mixed solution I obtained in the step three, and stirring to uniformly mix to obtain dressing preparation liquid; in the dressing preparation liquid, the mass percent of Tannin (TA) is 0.04%, the mass percent of iron (Fe) is 1.2%, and the mass percent of Ammonium Persulfate (APS) is 0.024%; the molecular weight of Tannic Acid (TA) is 220, the molecular weight of iron (Fe) is 270, and the molecular weight of Ammonium Persulfate (APS) is 228;
and step five, standing the dressing preparation liquid obtained in the step four at 22 ℃ for 1min to obtain the autocatalytic injectable hydrogel dressing (TFAEP) for treating bacterial infection.
The hydrogel dressing of this example performed substantially the same as example 1.
Example 4
This example provides a method of preparing an autocatalytic injectable hydrogel dressing for the treatment of bacterial infections, comprising the steps of:
firstly, dissolving polyvinyl alcohol (PVA) in water at the temperature of 80 ℃ until the PVA is completely clear to obtain a polyvinyl alcohol solution; in the polyvinyl alcohol solution, the mass percentage of polyvinyl alcohol (PVA) is 8%; the number average molecular weight of the polyvinyl alcohol (PVA) is 100000;
step two, providing the glycidyl methacrylate modified polylysine powder (EPL-GMA), which specifically comprises the following steps:
step 201, dissolving polylysine (EPL) in deionized water to obtain a polylysine solution with the mass percentage of 10%; the polylysine (EPL) has a molecular weight of 4000;
step 202, adding Glycidyl Methacrylate (GMA) into the polylysine solution at 83 ℃, and stirring for reaction for 6 hours; the molar ratio of the glycidyl methacrylate to the polylysine is 1:1; the molecular weight of the Glycidyl Methacrylate (GMA) is 142;
step 203, filtering the system reacted in the step 202 by using a dialysis bag for 4 days (the molecular weight cut-off of the dialysis bag is 1000), replacing 3 times per day of dialysis water, and freeze-drying after the dialysis is finished to obtain poly-lysine powder (EPL-GMA) modified by glycidyl methacrylate; the grafting rate of the poly-lysine modified by the glycidyl methacrylate is 40 percent; the freeze-drying may be freeze-drying at-80 ℃ for 3 days;
step three, adding the glycidyl methacrylate modified polylysine powder (EPL-GMA) obtained in the step two into the polyvinyl alcohol solution obtained in the step one, and stirring until the glycidyl methacrylate modified polylysine powder is completely dissolved to obtain a mixed solution I; the mass percentage content of the glycidyl methacrylate modified polylysine (EPL-GMA) in the mixed solution I is 10%;
step four, adding Tannic Acid (TA), iron (Fe) and Ammonium Persulfate (APS) into the mixed solution I obtained in the step three, and stirring to uniformly mix to obtain dressing preparation liquid; in the dressing preparation liquid, the mass percentage content of Tannic Acid (TA) is 0.025%, the mass percentage content of iron (Fe) is 0.75%, and the mass percentage content of Ammonium Persulfate (APS) is 0.026%; the molecular weight of Tannic Acid (TA) is 220, the molecular weight of iron (Fe) is 270, and the molecular weight of Ammonium Persulfate (APS) is 228;
and step five, standing the dressing preparation liquid obtained in the step four at 25 ℃ for 15min to obtain the autocatalytic injectable hydrogel dressing (TFAEP) for treating bacterial infection.
The hydrogel dressing of this example performed substantially the same as example 1.
Example 5
This example provides a method of preparing an autocatalytic injectable hydrogel dressing for the treatment of bacterial infections, comprising the steps of:
firstly, dissolving polyvinyl alcohol (PVA) in water at 83 ℃ until the PVA is completely clear to obtain a polyvinyl alcohol solution; in the polyvinyl alcohol solution, the mass percentage content of polyvinyl alcohol (PVA) is 9%; the polyvinyl alcohol (PVA) has a number average molecular weight of 90000;
step two, providing the glycidyl methacrylate modified polylysine powder (EPL-GMA), which specifically comprises the following steps:
step 201, dissolving polylysine (EPL) in deionized water to obtain a polylysine solution with the mass percentage of 10%; the polylysine (EPL) has a molecular weight of 4000;
step 202, adding Glycidyl Methacrylate (GMA) into the polylysine solution at 88 ℃, and stirring to react for 7 hours; the molar ratio of the glycidyl methacrylate to the polylysine is 1.5:1; the molecular weight of the Glycidyl Methacrylate (GMA) is 142;
step 203, filtering the system reacted in the step 202 by using a dialysis bag for 4 days (the molecular weight cut-off of the dialysis bag is 1000), replacing 3 times per day of dialysis water, and freeze-drying after the dialysis is finished to obtain poly-lysine powder (EPL-GMA) modified by glycidyl methacrylate; the grafting rate of the glycidyl methacrylate modified polylysine is 45 percent; the freeze-drying may be freeze-drying at-80 ℃ for 3 days;
step three, adding the glycidyl methacrylate modified polylysine powder (EPL-GMA) obtained in the step two into the polyvinyl alcohol solution obtained in the step one, and stirring until the glycidyl methacrylate modified polylysine powder is completely dissolved to obtain a mixed solution I; the mass percentage content of the glycidyl methacrylate modified polylysine (EPL-GMA) in the mixed solution I is 10%;
step four, adding Tannic Acid (TA), iron (Fe) and Ammonium Persulfate (APS) into the mixed solution I obtained in the step three, and stirring to uniformly mix to obtain dressing preparation liquid; in the dressing preparation liquid, the mass percent of Tannic Acid (TA) is 0.035%, the mass percent of iron (Fe) is 1.05%, and the mass percent of Ammonium Persulfate (APS) is 0.028%; the molecular weight of Tannic Acid (TA) is 220, the molecular weight of iron (Fe) is 270, and the molecular weight of Ammonium Persulfate (APS) is 228;
and step five, standing the dressing preparation liquid obtained in the step four at 15 ℃ for 3min to obtain the autocatalytic injectable hydrogel dressing (TFAEP) for treating bacterial infection.
The hydrogel dressing of this example performed substantially the same as example 1.
Example 6
This example provides a method of preparing an autocatalytic injectable hydrogel dressing for the treatment of bacterial infections, comprising the steps of:
firstly, dissolving polyvinyl alcohol (PVA) in water at the temperature of 88 ℃ until the PVA is completely clear to obtain a polyvinyl alcohol solution; in the polyvinyl alcohol solution, the mass percentage of polyvinyl alcohol (PVA) is 10%; the number average molecular weight of the polyvinyl alcohol (PVA) is 100000;
step two, providing the glycidyl methacrylate modified polylysine powder (EPL-GMA), which specifically comprises the following steps:
step 201, dissolving polylysine (EPL) in deionized water to obtain a polylysine solution with the mass percentage of 10%; the polylysine (EPL) has a molecular weight of 4000;
step 202, adding Glycidyl Methacrylate (GMA) into the polylysine solution at the temperature of 80 ℃, and stirring for reaction for 5 hours; the molar ratio of the glycidyl methacrylate to the polylysine is 2:1; the molecular weight of the Glycidyl Methacrylate (GMA) is 142;
step 203, filtering the system reacted in the step 202 by using a dialysis bag for 4 days (the molecular weight cut-off of the dialysis bag is 1000), replacing 3 times per day of dialysis water, and freeze-drying after the dialysis is finished to obtain poly-lysine powder (EPL-GMA) modified by glycidyl methacrylate; the grafting rate of the polylysine modified by the glycidyl methacrylate is 50 percent; the freeze-drying may be freeze-drying at-80 ℃ for 3 days;
step three, adding the glycidyl methacrylate modified polylysine powder (EPL-GMA) obtained in the step two into the polyvinyl alcohol solution obtained in the step one, and stirring until the glycidyl methacrylate modified polylysine powder is completely dissolved to obtain a mixed solution I; the mass percentage content of the glycidyl methacrylate modified polylysine (EPL-GMA) in the mixed solution I is 10%;
step four, adding Tannic Acid (TA), iron (Fe) and Ammonium Persulfate (APS) into the mixed solution I obtained in the step three, and stirring to uniformly mix to obtain dressing preparation liquid; in the dressing preparation liquid, the mass percentage of Tannic Acid (TA) is 0.01 percent, the mass percentage of iron (Fe) is 0.3 percent, and the mass percentage of Ammonium Persulfate (APS) is 0.03 percent; the molecular weight of Tannic Acid (TA) is 220, the molecular weight of iron (Fe) is 270, and the molecular weight of Ammonium Persulfate (APS) is 228;
and step five, standing the dressing preparation liquid obtained in the step four at 16 ℃ for 20min to obtain the autocatalytic injectable hydrogel dressing (TFAEP) for treating bacterial infection.
The hydrogel dressing of this example performed substantially the same as example 1.
Evaluation of Performance
FIG. 1 is a Fourier transform infrared spectrum of glycidyl methacrylate-modified polylysine (EPL-GMA) prepared in example 1, from which it can be seen in FIG. 1 that 802cm-1The characteristic peak is attributed to CH of methacrylate vinyl in GMA2Stretch, 1644cm-1Characteristic peaks at (a) were assigned to the C = C group, indicating successful synthesis of glycidyl methacrylate modified polylysine.
FIG. 2 is a Fourier transform infrared spectrum of the hydrogel dressing (TFAEP) prepared in example 1, as can be seen from 2. Appear at 3276cm-1And 3268cm-1The wide and strong absorption bands are respectively attributed to the hydroxyl symmetric stretching vibration of PVA and TA, and the-OH stretching peak of the hydrogel dressing (TFAEP) is shifted to a lower peak3253cm of bits-1The significant shift of the absorption band to lower wavenumbers indicates that stronger hydrogen bonds are formed between PVA and TA, demonstrating the successful synthesis of the hydrogels of the present invention.
Fig. 3 is XPS of the hydrogel dressing (TFAEP) prepared in example 1. Figure 3a shows that the content of O-C in the TA molecule is much higher than O = C, figure 3b shows that with Fe3+The content of C = O groups is significantly increased, indicating Fe3+Promoting the oxidation of the catechol group of the TA to a semiquinone/quinone group; the Fe 2p peak spectrum in FIG. 3c shows that Fe3+Is reduced to Fe2+The successful synthesis of the hydrogels of the present invention was demonstrated.
FIG. 4 is a scanning electron micrograph of the hydrogel dressing (TFAEP) prepared in example 1, and it can be seen from FIG. 4 that the pore size structure of the hydrogel of the present invention is uniform and dense.
Fig. 5 is a graph showing the injectability of the hydrogel dressing (TFAEP) prepared in example 1, and it can be seen from fig. 5 that the hydrogel of the present invention has good injectability and is expected to fill the whole wound surface when injected to the wound surface in clinical application.
FIG. 6 is a graph showing the adhesion performance of the hydrogel dressing (TFAEP) prepared in example 1, wherein 6a is a graph showing the adhesion of hydrogel to plastic, 6b is a graph showing the adhesion to glass, and 6c is a graph showing the adhesion to steel, indicating that the hydrogel material of the present invention has good adhesion.
Fig. 7 is a graph showing the antibacterial performance of the hydrogel dressing (TFAEP) prepared in example 1, and the method for evaluating the antibacterial performance includes: suspending bacteria (10)7CFU/mL) were divided into 5 groups of 1mL each, the first group was used as a blank control group, and TFAEP hydrogel dressing, TFAEP hydrogel dressing + H were applied to the remaining four groups, respectively2O2TFAEP hydrogel dressing + NIR and TFAEP hydrogel dressing + NIR + H2O2After 30 minutes of incubation, 100. Mu.l of the diluted bacterial suspension was spread on an agar plate, incubated at 37 ℃ for 24 hours, and the number of colonies was observed to calculate the bacterial survival rate. The hydrogel dressing in the NIR group was at 808nm (1.0W/cm)2) After 10 minutes exposure to radiation. Plate counting was performed using imagej software to determine the resistance of hydrogels to photothermal and peroxidase activitiesAnd (4) bacterial capacity. The survival = (OD) was calculated by measuring the Optical Density (OD) at 600nm using a microplate reader for the resulting bacterial suspensionTest specimen-ODBlank space)/(ODControl of-ODBlank space). As can be seen from fig. 7, the antimicrobial activity of the hydrogel dressing was significantly improved compared to the control group, which may be derived from the inherent properties of EPLMA and TA; dressings containing TFAEP hydrogel and H2O2The activity increase in the group may be based on a further combination of POD-like activities. The antibacterial ability of the TFAEP + NIR group is obviously enhanced, which shows that TFAEP and near infrared can act synergistically to further improve the sterilization effect. TFAEP + NIR + H2O2The groups have no bacteria, and the PTT and POD activities and the comprehensive action of the tannic acid and the polylysine in the hydrogel dressing can kill microorganisms, so that the hydrogel dressing has good antibacterial capacity.
Fig. 8 is a graph of photothermal performance of the hydrogel dressing (TFAEP) prepared in example 1, the test method for photothermal performance comprising: the sample was placed in 1mL of ultrapure water, irradiated with a 808nm near infrared laser, and the solution temperature was recorded every 30s, and the results are shown in FIG. 8. As can be seen from fig. 8a, as the content of Fe in the dressing increases, the temperature of the solution increases, indicating that the hydrogel dressing of the present invention has excellent photothermal conversion capability; as can be seen from FIG. 8b, the solution temperature increases with increasing laser power. Fig. 8c is a graph of photothermal performance under 5 laser switch cycles, indicating that the hydrogel dressing (TFAEP) of the present invention has good photothermal conversion capability; the preparation method of the hydrogel dressing with different Fe contents in FIG. 8a is substantially the same as that of example 1, and only the addition amount of iron (Fe) in the fourth step is correspondingly adjusted.
Fig. 9 is a graph of peroxidase-like performance of the hydrogel dressing (TFAEP) prepared in example 1, evaluated by the ability to oxidize 3, 5-Tetramethylbenzidine (TMB) to oxTMB in a Phosphate Buffered Saline (PBS) solution (pH = 4.0). The specific test method comprises the following steps: placing the hydrogel dressing in the container containing H2O2And H is not contained in the TMB solution2O2The color reaction of oxTMB at 652nm was measured by UV-visible absorbance for a predetermined time in the TMB solution of (1). According toAs can be seen in fig. 9, the absorbance varied with ferric ion concentration, temperature and pH, indicating that the hydrogel dressing (TFAEP) had good peroxidase-like activity.
Fig. 10 is a graph of the antioxidant properties of the hydrogel dressing (TFAEP) prepared in example 1, the antioxidant properties test method including: and (3) soaking the hydrogel in a DPPH solution, standing at room temperature for 20min, sucking a supernatant to determine a full-wavelength scanning curve and acquiring the absorbance of the scanning curve at 517nm to obtain the DPPH removal experiment test effect. Dissolving 3mg of PTIO powder in 20mL of water, adding hydrogel, reacting for 2h in a water bath at 37 ℃, taking supernatant, determining a full-wavelength scanning curve, and obtaining the absorbance of the supernatant at 557nm to obtain the PTIO removal experiment test result. As can be seen from fig. 10, the hydrogel of the present invention can effectively scavenge RNS and ROS, indicating that the hydrogel dressing has good oxidation resistance.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and any simple modifications, changes and equivalent structural changes made to the above embodiment according to the technical spirit of the present invention still fall within the protection scope of the technical solution of the present invention.
Claims (6)
1. A method of preparing an autocatalytic injectable hydrogel dressing for the treatment of bacterial infections, comprising: adding tannic acid, iron and ammonium persulfate into a polyvinyl alcohol solution containing glycidyl methacrylate modified polylysine to obtain a dressing preparation solution, and standing the dressing preparation solution at 15-25 ℃ for 1-20 min to obtain the autocatalytic injectable hydrogel dressing for treating bacterial infection; the grafting rate of the glycidyl methacrylate modified polylysine is 40-50%; the dressing preparation liquid contains 0.01-0.04 wt% of tannic acid, 0.3-1.2 wt% of iron and 0.02-0.03 wt% of ammonium persulfate.
2. The method for preparing an autocatalytic injectable hydrogel dressing for treating bacterial infection according to claim 1, wherein the glycidyl methacrylate modified polylysine is glycidyl methacrylate modified polylysine prepared by stirring and reacting a solution of glycidyl methacrylate and polylysine at a temperature of 80-90 ℃ for 5-7 h.
3. The method for preparing an autocatalytic injectable hydrogel dressing for the treatment of bacterial infection according to claim 2, wherein the molar ratio of glycidyl methacrylate to polylysine is (1-2): 1.
4. the method for preparing an autocatalytic injectable hydrogel dressing for treatment of bacterial infection according to claim 2, wherein said polylysine has a molecular weight of 4000.
5. The method for preparing an autocatalytic injectable hydrogel dressing for treating bacterial infection according to claim 1, wherein the polyvinyl alcohol solution containing the glycidyl methacrylate modified polylysine is prepared by adding glycidyl methacrylate modified polylysine into a polyvinyl alcohol solution, the polyvinyl alcohol solution contains 5-10% by weight of polyvinyl alcohol, and the polyvinyl alcohol solution contains 10% by weight of glycidyl methacrylate modified polylysine.
6. The method for preparing an autocatalytic injectable hydrogel dressing for treatment of bacterial infection according to claim 5 wherein said polyvinyl alcohol solution has a molecular weight of 90000.
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