Photocatalytic hydrogen peroxide production liquid band-aid and preparation method thereof
By preparing a liquid bandage containing a zinc-based semiconductor photocatalyst modified with phenolic organic compounds, hydrogen peroxide is generated through photocatalysis to achieve highly efficient sterilization. This solves the problems of irritating odor and unsatisfactory sterilization effect of existing liquid bandages, and provides an environmentally friendly and convenient wound care solution.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- JIANGSU UNIV
- Filing Date
- 2025-02-24
- Publication Date
- 2026-05-12
AI Technical Summary
Existing liquid bandages have a strong irritating odor, unsatisfactory sterilization effect, and are not environmentally friendly. Traditional bandages cannot effectively cover large or irregular wounds, have poor breathability, and are not environmentally friendly due to their single-use nature.
A liquid bandage that generates hydrogen peroxide through photocatalysis was prepared using a zinc-based semiconductor photocatalyst modified with phenolic organic compounds, film-forming materials of chitosan hydrochloride and nitrocellulose, hyaluronic acid moisturizer, and volatile solvents of ethanol and physiological saline. The bandage generates hydrogen peroxide through light irradiation to achieve sterilization.
It achieves efficient, environmentally friendly, and long-lasting sterilization, and can adjust hydrogen peroxide production according to the severity of the wound, improving wound care and simplifying its use.
Smart Images
Figure CN119971128B_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of medical dressing technology, and specifically discloses a liquid bandage that produces hydrogen peroxide through photocatalysis and its preparation method. Background Technology
[0002] Band-aids are widely used medical supplies in daily life, mainly used to protect wounds and promote healing. However, traditional band-aids usually consist of dressings, adhesive tape, and release liner, and have obvious limitations: 1) limited disinfection effect, making it difficult to provide continuous antibacterial protection; 2) fixed shape and size, unable to effectively cover large or irregularly shaped wounds; 3) poor breathability, which is not conducive to wound healing; 4) single-use, which is not environmentally friendly.
[0003] To address the shortcomings of traditional adhesive bandages, many pharmaceutical companies and research institutions have developed liquid adhesive bandages. Liquid adhesive bandages are not limited by the shape of the wound; they can be directly applied or sprayed onto the wound surface to form a protective film. Furthermore, they can carry different active ingredients, are waterproof and breathable, and solve problems such as redness and discomfort caused by traditional adhesive bandages. For these reasons, liquid adhesive bandages have become a hot research topic.
[0004] However, some commercially available and patented liquid bandages still suffer from problems such as strong irritating odors and unsatisfactory bactericidal effects. For example, patent CN116271205A describes a liquid bandage containing black phosphorus nanosheets and its preparation method. This bandage includes a film-forming substance, solvent, adhesive aid, local anesthetic, antibacterial agent, anti-inflammatory agent, moisturizer, and fragrance. The antibacterial agent is a mixture of black phosphorus nanosheets and benzalkonium chloride. Although this liquid bandage containing black phosphorus nanosheets is convenient to use and forms a film quickly, the use of antibacterial materials such as benzalkonium chloride can cause allergic reactions and toxic side effects. Patent CN110124095A describes an antibacterial liquid bandage and its preparation method. This antibacterial liquid bandage includes doxycycline, nitrocellulose, Bletilla striata extract, plasticizer, liquid solvent, and preservative. The doxycycline added to this liquid bandage acts as an antibacterial agent, but the dosage is large and the effective duration is short.
[0005] Therefore, developing a new type of highly efficient, environmentally friendly, and long-lasting adhesive bandage is an important issue that urgently needs to be addressed. Summary of the Invention
[0006] To address the shortcomings of existing technologies, the purpose of this application is to provide a photocatalytic hydrogen peroxide-producing gel bandage and its preparation method. By selecting specific materials and combining them with corresponding preparation methods, a photocatalytic hydrogen peroxide-producing gel bandage is obtained, which not only has antibacterial and bactericidal effects and promotes wound healing, but also improves wound care effects, enhances user experience, and solves the technical problems existing in current bandages.
[0007] In one aspect, the present invention provides a liquid bandage for photocatalytic hydrogen peroxide production, the components of which include 0.1-5 wt% of a zinc-based semiconductor photocatalyst modified with phenolic organic compounds, 2-10 wt% of a film-forming material, 0.1-3 wt% of a humectant, and 82-97.8 wt% of a mixed volatile solvent.
[0008] The film-forming material is a mixture of chitosan hydrochloride and nitrocellulose.
[0009] The moisturizer is hyaluronic acid;
[0010] The volatile solvent is a mixture of ethanol and physiological saline.
[0011] The zinc-based semiconductor photocatalyst modified with phenolic organic compounds is a photocatalyst capable of generating hydrogen peroxide, including but not limited to: nitrogen-doped zinc oxide modified with phenol, zinc oxide modified with phenol, ZnO / ZnO2 complex modified with phenol, zinc single-atom anchored carbon nitride modified with phenol, zinc sulfide modified with phenol, nitrogen-doped zinc oxide modified with o-methoxyphenol, oxygen-deficient zinc oxide modified with o-methoxyphenol, ZnO / ZnO2 complex modified with o-methoxyphenol, and nitrogen-doped zinc oxide modified with p-methoxyphenol.
[0012] Furthermore, the mass ratio of chitosan hydrochloride to nitrocellulose in the film-forming material is (1-2):(1-3). Even further, the mass ratio of chitosan hydrochloride to nitrocellulose in the film-forming material is 1:1.5-2.
[0013] Furthermore, the volume ratio of ethanol to physiological saline in the volatile solvent is (1-3):(1-8). Even further, the volume ratio of ethanol to physiological saline in the volatile solvent is 1:1.
[0014] Furthermore, the moisturizer is hyaluronic acid with a molecular weight of 800,000 to 2,200,000 Daltons.
[0015] Furthermore, the zinc-based semiconductor photocatalyst modified with phenolic organic compounds is preferably nitrogen-doped zinc oxide modified with o-methoxyphenol.
[0016] Furthermore, the method for preparing the o-methoxyphenol-modified nitrogen-doped zinc oxide includes the following steps:
[0017] 1) Preparation of nitrogen-doped zinc oxide
[0018] Thiourea, anhydrous zinc acetate, and ethylenediaminetetraacetic acid were added sequentially to deionized water and stirred until homogeneous to obtain a mixture. The mixture was then transferred to a reaction vessel for hydrothermal reaction. After the reaction was completed, the mixture was centrifuged, washed, and dried to obtain a nitrogen-doped zinc oxide precursor. Subsequently, the nitrogen-doped zinc oxide precursor was calcined to obtain nitrogen-doped zinc oxide.
[0019] 2) Nitrogen-doped zinc oxide modified with o-methoxyphenol
[0020] Ethanol was stirred in a water bath while nitrogen-doped zinc oxide obtained in step 1) was added to obtain a uniform suspension. Then, o-methoxyphenol was added dropwise to the suspension and the water bath conditions were maintained until the liquid evaporated completely, thus obtaining nitrogen-doped zinc oxide modified with o-methoxyphenol.
[0021] In step 1) of this invention:
[0022] The molar ratio of thiourea, anhydrous zinc acetate, and ethylenediaminetetraacetic acid is 4:4:0.1–3;
[0023] The mass ratio of thiourea to deionized water is 1:10 to 300;
[0024] The hydrothermal reaction temperature is 150–180℃, and the hydrothermal reaction time is 6–12 hours;
[0025] The calcination temperature is 380–950℃, and the calcination time is 1–12 hours.
[0026] In step 2) of this invention:
[0027] The water bath temperature is 40-45℃;
[0028] The mass ratio of nitrogen-doped zinc oxide to ethanol is 1:10 to 100;
[0029] The mass ratio of o-methoxyphenol to nitrogen-doped zinc oxide is 1:5 to 30.
[0030] In another aspect of the present invention, a method for preparing the liquid adhesive bandage as described above is provided, the method comprising the following steps:
[0031] 1) First, the mixed volatile solvent is divided into two parts, denoted as solvent A and solvent B; the zinc-based semiconductor photocatalyst modified with phenolic organic compounds is ground into powder to obtain zinc-based semiconductor powder modified with phenolic organic compounds; then the zinc-based semiconductor powder modified with phenolic organic compounds is added to solvent A, stirred and then ultrasonically treated to obtain a uniform mixture A.
[0032] 2) Grind the prescribed amount of film-forming material into powder to obtain film-forming material powder; then add the film-forming material powder to solvent B and stir evenly to obtain mixture B;
[0033] 3) Pour the mixture A obtained in step 1) into the mixture B obtained in step 2), stir well, and obtain mixture C;
[0034] 4) Add the prescribed amount of moisturizer to the mixture C obtained in step 3), and then perform ultrasonic treatment under stirring conditions to form a uniform and stable solution, which is the liquid bandage.
[0035] 5) Fill the liquid bandage obtained in step 4) into a spray bottle or other storage container and seal it to obtain the finished product.
[0036] In step 1) of this invention:
[0037] The volume ratio of solvent A to solvent B is 1:1; the stirring time is 20-30 minutes.
[0038] The conditions for ultrasonic treatment are: power 300-1000 watts, time 3-30 minutes.
[0039] In step 2):
[0040] The stirring time is 20-30 minutes;
[0041] In step 4):
[0042] The conditions for ultrasonic treatment are: power 300-1000 watts, time 3-30 minutes.
[0043] The beneficial effects of this application are:
[0044] 1. The liquid bandage of the present invention has a simple preparation method, the finished product can be carried around, and it is simple and convenient to use.
[0045] 2. The liquid bandage prepared by this invention, when applied to the surface of a wound, can catalyze the generation of hydrogen peroxide from air and wound tissue fluid under light irradiation, thereby achieving the effect of antibacterial and bactericidal action.
[0046] 3. The liquid wound dressing prepared by this invention can be applied in different amounts according to the severity of the wound, thereby achieving the effect of automatically adjusting the hydrogen peroxide production.
[0047] 4. The liquid wound prepared by this invention has long-term stability and long effective action time, and has continuous bactericidal properties within 24 hours. Attached Figure Description
[0048] Figure 1 This is a scanning electron microscope image of nitrogen-doped zinc oxide modified with o-methoxyphenol prepared in Example 1.
[0049] Figure 2 This is a scanning X-ray electron diffraction pattern of nitrogen-doped zinc oxide modified with o-methoxyphenol prepared in Example 1.
[0050] Figure 3 This is an optical microscope image of nitrogen-doped zinc oxide modified with phenol as described in Example 2.
[0051] Figure 4 This is a graph showing the photocatalytic hydrogen peroxide production performance of the liquid bandage in Example 13.
[0052] Figure 5 This is a graph showing the photocatalytic hydrogen peroxide production performance of the liquid bandage in Example 14.
[0053] Figure 6 The diagram shows the antibacterial and bactericidal efficacy of the liquid bandage in Example 15; Figure A shows the growth of Escherichia coli in the experimental group; Figure B shows the growth of Escherichia coli in the control group. Detailed Implementation
[0054] The present invention will be further described below with reference to the accompanying drawings and specific embodiments, but the scope of protection of the present invention is not limited thereto.
[0055] The present invention will be described in detail below through specific embodiments. It must be noted that these embodiments are for illustrative purposes only and not for limiting the invention. Unless otherwise specified, the reagents or materials mentioned in this invention can be prepared by conventional methods or purchased commercially.
[0056] Example 1: Preparation of nitrogen-doped zinc oxide modified with o-methoxyphenol
[0057] 1) 7.612 mg of thiourea, 18.347 mg of anhydrous zinc acetate, and 1.5 mg of ethylenediaminetetraacetic acid were slowly added sequentially to a 500 mL beaker containing 300 mL of deionized water. After stirring evenly, the mixture in the beaker was transferred to a reaction vessel for hydrothermal reaction at 160 °C for 8 hours. After the reaction, the reaction vessel was allowed to cool naturally to room temperature. The mixture in the reaction vessel was centrifuged (10000 r / min, 15 min), and the lower precipitate was collected. The precipitate was then washed three times with deionized water and ethanol, respectively. The washed solid precipitate was dried in a vacuum oven at 50 °C for 24 hours to obtain the nitrogen-doped zinc oxide precursor. The nitrogen-doped zinc oxide precursor was then calcined in a muffle furnace at 500 °C for 2 hours to obtain nitrogen-doped zinc oxide.
[0058] 2) Slowly add 100 mL of ethanol to a 250 mL round-bottom flask, then place it in a 40 °C water bath. While stirring, slowly add 2 g of the nitrogen-doped zinc oxide obtained in step 1) to obtain a uniform suspension. Then, slowly add 0.2 mg of o-methoxyphenol to the above suspension, and maintain the 40 °C water bath until the liquid in the flask evaporates completely. The solid product obtained is the nitrogen-doped zinc oxide modified with o-methoxyphenol. Figure 1 This is a scanning electron microscope image of the nitrogen-doped zinc oxide modified with o-methoxyphenol. Figure 2 This is a scanning X-ray electron diffraction pattern of nitrogen-doped zinc oxide modified with o-methoxyphenol.
[0059] Example 2: Preparation of phenol-modified nitrogen-doped zinc oxide
[0060] In this embodiment, o-methoxyphenol was replaced with an equal amount of phenol, and the remaining steps were the same as in Example 1, finally yielding nitrogen-doped zinc oxide modified with phenol. Figure 3 This is an optical microscope image of nitrogen-doped zinc oxide modified with phenol.
[0061] Example 3: Preparation of the liquid bandage of the present invention
[0062] I. The components of the liquid wound dressing (based on a total weight of 100 wt%) include:
[0063] 5.0 wt% of a zinc-based semiconductor photocatalyst modified with phenolic organic compounds (nitrogen-doped zinc oxide modified with o-methoxyphenol), 5.0 wt% of a film-forming material (chitosan hydrochloride and nitrocellulose in a mass ratio of 1:2), 1.0 wt% of a humectant (hyaluronic acid with a Dalton content of 1,000,000 to 2,000,000), and 89.0 wt% of a mixed volatile solvent (ethanol and physiological saline mixed in equal volumes).
[0064] II. Preparation method:
[0065] Select the dosage according to the proportions of each component in the liquid bandage, and divide the mixed volatile solvent into two parts, denoted as solvent A and solvent B; perform the following operations:
[0066] 1) Grind the nitrogen-doped zinc oxide modified with o-methoxyphenol into powder to obtain o-methoxyphenol-modified nitrogen-doped zinc oxide powder; then add the o-methoxyphenol-modified nitrogen-doped zinc oxide powder into solvent A, stir for 30 minutes, and then sonicate at 500 watts for 10 minutes to obtain a uniform mixture.
[0067] 2) Chitosan hydrochloride and nitrocellulose are mixed and ground into powder at a mass ratio of 1:2 to obtain a mixed powder of chitosan hydrochloride and nitrocellulose; then the mixed powder of chitosan hydrochloride and nitrocellulose is added to solvent B and stirred for 30 minutes to obtain a uniform mixture.
[0068] 3) Slowly pour the mixture obtained in step 1) into the mixture obtained in step 2), stir for 30 minutes, and a homogeneous mixture is obtained;
[0069] 4) Finally, slowly add hyaluronic acid to the mixture obtained in step 3), continue stirring and supplement with ultrasonic treatment for 10 minutes (power 500 watts) to form a uniform and stable liquid bandage.
[0070] 5) Fill the liquid bandage obtained in step (4) into a spray bottle or other suitable storage container and seal it to obtain the finished product.
[0071] Example 4:
[0072] Same as Example 3, except that the components are as follows:
[0073] The liquid wound dressing comprises: 0.1 wt% of a zinc-based semiconductor photocatalyst modified with phenolic organic compounds (nitrogen-doped zinc oxide modified with o-methoxyphenol), 10 wt% of a film-forming material (chitosan hydrochloride and nitrocellulose in a mass ratio of 1:2), 3 wt% of a moisturizer (hyaluronic acid with a concentration of 800,000 to 1,200,000 Daltons), and 86.9 wt% of a mixed volatile solvent (ethanol and physiological saline mixed in equal volumes).
[0074] Example 5:
[0075] Same as Example 3, except that the components are as follows:
[0076] The liquid wound dressing comprises: 5 wt% of a zinc-based semiconductor photocatalyst modified with phenolic organic compounds (nitrogen-doped zinc oxide modified with o-methoxyphenol), 6 wt% of a film-forming material (chitosan hydrochloride and nitrocellulose in a mass ratio of 1:2), 0.1 wt% of a moisturizer (hyaluronic acid with a mass of 1,000,000 to 1,800,000 Daltons), and 88.9 wt% of a mixed volatile solvent (ethanol and physiological saline mixed in equal volumes).
[0077] Example 6:
[0078] Same as Example 3, except that the components are as follows:
[0079] The liquid wound dressing comprises: 2.5 wt% of a zinc-based semiconductor photocatalyst modified with phenolic organic compounds (nitrogen-doped zinc oxide modified with o-methoxyphenol), 2 wt% of a film-forming material (chitosan hydrochloride and nitrocellulose in a mass ratio of 1:2), 2 wt% of a moisturizer (1,000,000 to 2,000,000 Dalton hyaluronic acid), and 93.5 wt% of a mixed volatile solvent (ethanol and physiological saline mixed in equal volumes).
[0080] Example 7:
[0081] Same as Example 3, except that the components are as follows:
[0082] The liquid wound dressing comprises: 3 wt% of a zinc-based semiconductor photocatalyst modified with phenolic organic compounds (phenol-modified nitrogen-doped zinc oxide), 2 wt% of a film-forming material (chitosan hydrochloride and nitrocellulose in a mass ratio of 1:2), 2 wt% of a moisturizer (hyaluronic acid with a volume ratio of 800,000 to 2,200,000 Daltons), and 93 wt% of a mixed volatile solvent (ethanol and physiological saline mixed in a volume ratio of 1:2).
[0083] Example 8:
[0084] Same as Example 3, except that the components are as follows:
[0085] The liquid wound dressing comprises: 2.5 wt% of a phenolic organic modified zinc-based semiconductor photocatalyst (nitrogen-doped zinc oxide modified with p-methoxyphenol), 3 wt% of a film-forming material (chitosan hydrochloride and nitrocellulose in a mass ratio of 1:2), 1.3 wt% of a moisturizer (hyaluronic acid with a concentration of 800,000 to 2,000,000 Daltons), and 93.2 wt% of a mixed volatile solvent (ethanol and physiological saline in a volume ratio of 2.5:1). The preparation method of the nitrogen-doped zinc oxide modified with p-methoxyphenol is the same as in Example 1, except that o-methoxyphenol is replaced with an equal amount of p-methoxyphenol.
[0086] Example 9:
[0087] Same as Example 3, except that the components are as follows:
[0088] The liquid wound dressing comprises: 2.5 wt% of a zinc-based semiconductor photocatalyst modified with phenolic organic compounds (a combination of nitrogen-doped zinc oxide modified with o-methoxyphenol and oxygen-deficient zinc oxide modified with o-methoxyphenol in a mass ratio of 1:1), 9 wt% of a film-forming material (chitosan hydrochloride and nitrocellulose in a mass ratio of 1:2), 2.5 wt% of a moisturizer (hyaluronic acid with a mass ratio of 1,000,000 to 2,000,000 Daltons), and 86 wt% of a mixed volatile solvent (ethanol and physiological saline mixed in a volume ratio of 3:1).
[0089] The preparation method of oxygen-deficient zinc oxide modified with o-methoxyphenol is as follows: 0.1M zinc nitrate hexahydrate (Zn(NO3)2·6H2O) is dissolved in 100mL of deionized water and stirred until completely dissolved. While stirring, 0.1M sodium borohydride (NaBH4) solution is added dropwise until the solution becomes transparent. The mixed solution is heated at 80℃ for 2 hours to promote the formation of oxygen vacancies. The resulting precipitate is collected by vacuum filtration and washed several times with deionized water to remove residual reactants. The washed precipitate is dried at 60℃ for 12 hours to obtain oxygen-deficient zinc oxide powder. The dried zinc oxide powder is dispersed in 100mL of ethanol, and o-methoxyphenol (in equal amounts) is added and stirred at room temperature for 24 hours to complete the surface modification. The modified zinc oxide is collected by vacuum filtration and dried at 60℃ for 12 hours to obtain o-methoxyphenol-modified oxygen-deficient zinc oxide.
[0090] Example 10:
[0091] Same as Example 3, except that the components are as follows:
[0092] The liquid wound dressing comprises: 1.5 wt% of a phenolic organic modified zinc-based semiconductor photocatalyst (a combination of phenol-modified ZnO / ZnO2 complex and o-methoxyphenol-modified oxygen-deficient zinc oxide in a mass ratio of 2:1), 6 wt% of a film-forming material (chitosan hydrochloride and nitrocellulose in a mass ratio of 1:2), 2.5 wt% of a moisturizer (hyaluronic acid with a mass of 800,000 to 2,200,000 Daltons), and 90 wt% of a mixed volatile solvent (ethanol and physiological saline in a volume ratio of 3:1). The phenol modification method is the same as in Example 1, except that the modifier is replaced by an equal amount of phenol instead of o-methoxyphenol. The preparation of o-methoxyphenol-modified oxygen-deficient zinc oxide is the same as in Example 9.
[0093] Example 11:
[0094] Same as Example 3, except that the components are as follows:
[0095] The liquid wound dressing comprises: 1 wt% of a phenolic organic modified zinc-based semiconductor photocatalyst (a combination of nitrogen-doped zinc oxide modified with o-methoxyphenol and nitrogen-doped zinc oxide modified with p-methoxyphenol in a mass ratio of 1:3), 8.5 wt% of a film-forming material (chitosan hydrochloride and nitrocellulose in a mass ratio of 1:2), 2.5 wt% of a moisturizer (hyaluronic acid with a mass of 800,000 to 1,000,000 Daltons), and 88 wt% of a mixed volatile solvent (ethanol and physiological saline mixed in a volume ratio of 3:1); wherein the preparation of the nitrogen-doped zinc oxide modified with p-methoxyphenol is the same as in Example 8.
[0096] Example 12:
[0097] Same as Example 3, except that the components are as follows:
[0098] The liquid wound dressing comprises: 2.5 wt% of a zinc-based semiconductor photocatalyst modified with phenolic organic compounds (a combination of nitrogen-doped zinc oxide modified with o-methoxyphenol and nitrogen-doped zinc oxide modified with phenol in a mass ratio of 1:3), 5 wt% of a film-forming material (chitosan hydrochloride and nitrocellulose in a mass ratio of 1:2), 1.2 wt% of a moisturizer (800,000–2,200,000 Dalton hyaluronic acid), and 91.3 wt% of a mixed volatile solvent (ethanol and physiological saline mixed in equal volumes).
[0099] Example 13: Study on the photocatalytic hydrogen peroxide production performance of the liquid bandage described in this invention
[0100] 1) Spray 100 μL of the liquid bandage prepared in Example 3 onto a glass slide with a width of 1 cm and a length of 2 cm. After air drying for 24 hours, peel off the film from the glass slide.
[0101] 2) Add the film obtained in step 1) to a 50 mL beaker containing 20 mL of deionized water, stir for 30 minutes, and then place the beaker under LED light with a wavelength of 405 nm for 3 hours.
[0102] 3) Detect the concentration of hydrogen peroxide generated.
[0103] The results are as follows Figure 4 As shown, under 405nm LED light irradiation, the concentration of hydrogen peroxide gradually increases with the increase of light irradiation time, showing a good linear relationship; and after 3 hours, the concentration of hydrogen peroxide generated is already higher than 300mol / L; indicating that the prepared liquid bandage can effectively generate hydrogen peroxide under light irradiation.
[0104] Example 14: Study on the photocatalytic hydrogen peroxide production performance of the liquid bandage described in this invention
[0105] 1) Spray 100 μL of the liquid bandage prepared in Examples 4-12 onto glass slides with a width of 1 cm and a length of 2 cm. After air drying for 24 hours, peel off the film from the glass slides.
[0106] 2) Add the films obtained in step 1) to 50 mL beakers containing 20 mL of deionized water, stir for 30 minutes, and then place the beakers under LED light with a wavelength of 405 nm for 3 hours.
[0107] 3) Detect the concentration of hydrogen peroxide generated.
[0108] The results are as follows Figure 5 As shown, after 3 hours of irradiation with 405nm LED light, the concentration of hydrogen peroxide generated was higher than 180mol / L; indicating that the prepared liquid bandage can generate hydrogen peroxide under light irradiation, and the effect is significant.
[0109] Example 15: Study on the antibacterial and bacteriostatic effects of the liquid bandage described in this invention (taking Example 3 as an example)
[0110] 1) Apply 100 μL of the liquid bandage prepared in Example 3 onto the surface of an agar plate;
[0111] 2) Spread 100 μL of Escherichia coli culture onto the surface of the agar plate treated in step 1), and irradiate the culture dish with an LED with a wavelength of 405 nm for 3 hours.
[0112] 3) Then incubate at 37℃ for 24 hours, observe the growth of E. coli in the culture dish, and record and photograph the results.
[0113] Comparative example:
[0114] 1) Spread 100 μL of solvent onto the surface of an agar plate, wherein the solvent is a mixture of ethanol and physiological saline in a volume ratio of 1:1;
[0115] 2) Spread 100 μL of Escherichia coli culture onto the surface of the agar plate treated in step 1), and irradiate the culture dish with an LED with a wavelength of 405 nm for 3 hours.
[0116] 3) Then incubate at 37℃ for 24 hours, observe the growth of E. coli in the culture dish, and record and photograph the results.
[0117] Note: Agar plates should be autoclaved at 121°C for 15 minutes before use.
[0118] The results are as follows Figure 6As shown in Figure A, E. coli growth after applying the liquid adhesive bandage (experimental group); and B, E. coli growth without applying the liquid adhesive bandage (control group). The results are clear: while the control group was covered with colonies, the experimental group treated with the liquid adhesive bandage of this invention showed no colony growth, indicating that the liquid adhesive bandage prepared by this invention has good antibacterial properties.
[0119] Note: The above embodiments are only used to illustrate the present invention and are not intended to limit the technical solutions described in the present invention. Therefore, although the present invention has been described in detail with reference to the above embodiments, those skilled in the art should understand that modifications or equivalent substitutions can still be made to the present invention. All technical solutions and improvements that do not depart from the spirit and scope of the present invention should be covered within the scope of the claims of the present invention.
Claims
1. A liquid bandage for photocatalytic hydrogen peroxide production, characterized in that, The liquid bandage component comprises 0.1-5 wt% of a zinc-based semiconductor photocatalyst modified with phenolic organic compounds, 2-10 wt% of a film-forming material, 0.1-3 wt% of a humectant, and 82-97.8 wt% of a mixed volatile solvent. The film-forming material is a mixture of chitosan hydrochloride and nitrocellulose. The moisturizer is hyaluronic acid; The mixed volatile solvent is a mixture of ethanol and physiological saline; The zinc-based semiconductor photocatalyst modified with phenolic organic compounds is a photocatalyst capable of generating hydrogen peroxide, and is one or more of the following: nitrogen-doped zinc oxide modified with phenol, phenol-modified ZnO / ZnO2 composite, nitrogen-doped zinc oxide modified with o-methoxyphenol, oxygen-deficient zinc oxide modified with o-methoxyphenol, and nitrogen-doped zinc oxide modified with p-methoxyphenol. The mass ratio of chitosan hydrochloride to nitrocellulose in the film-forming material is (1~2):(1~3); the volume ratio of ethanol to physiological saline in the volatile solvent is (1~3):(1~8); and the moisturizer is hyaluronic acid with a molecular weight of 800,000~2,200,000 Daltons.
2. The liquid bandage for photocatalytic hydrogen peroxide production according to claim 1, characterized in that, The zinc-based semiconductor photocatalyst modified with phenolic organic compounds is nitrogen-doped zinc oxide modified with o-methoxyphenol.
3. The liquid bandage for photocatalytic hydrogen peroxide production according to claim 1, characterized in that, The mass ratio of chitosan hydrochloride to nitrocellulose in the film-forming material is 1:1.5~2; the volume ratio of ethanol to physiological saline in the volatile solvent is 1:
1.
4. The liquid bandage for photocatalytic hydrogen peroxide production according to claim 1, characterized in that, The method for preparing the o-methoxyphenol-modified nitrogen-doped zinc oxide includes the following steps: 1) Preparation of nitrogen-doped zinc oxide; Thiourea, anhydrous zinc acetate, and ethylenediaminetetraacetic acid were added sequentially to deionized water and stirred until homogeneous to obtain a mixture. The mixture was then transferred to a reaction vessel for hydrothermal reaction. After the reaction was completed, the mixture was centrifuged, washed, and dried to obtain a nitrogen-doped zinc oxide precursor. Subsequently, the nitrogen-doped zinc oxide precursor was calcined to obtain nitrogen-doped zinc oxide. 2) Nitrogen-doped zinc oxide modified with o-methoxyphenol; Ethanol was stirred in a water bath while nitrogen-doped zinc oxide obtained in step 1) was added to obtain a uniform suspension. Then, o-methoxyphenol was added dropwise to the suspension and the water bath conditions were maintained until the liquid evaporated completely. The resulting solid product was o-methoxyphenol-modified nitrogen-doped zinc oxide.
5. A liquid bandage for photocatalytic hydrogen peroxide production according to claim 4, characterized in that, In step 1): The molar ratio of thiourea, anhydrous zinc acetate, and ethylenediaminetetraacetic acid is 4:4:0.1~3; The mass ratio of thiourea to deionized water is 1:10~300; The hydrothermal reaction temperature is 150~180℃, and the hydrothermal reaction time is 6~12 hours; The calcination temperature is 380~950℃, and the calcination time is 1~12 hours.
6. A liquid bandage for photocatalytic hydrogen peroxide production according to claim 4, characterized in that, In step 2): The water bath temperature is 40-45℃; The mass ratio of nitrogen-doped zinc oxide to ethanol is 1:10~100; The mass ratio of o-methoxyphenol to nitrogen-doped zinc oxide is 1:5~30.
7. The liquid bandage for photocatalytic hydrogen peroxide production according to any one of claims 1-6, characterized in that, The liquid bandage forms a thin film after being applied to the wound surface.
8. The method for preparing the liquid bandage for photocatalytic hydrogen peroxide production according to any one of claims 1-6, characterized in that, The steps are as follows: 1) First, the mixed volatile solvent is divided into two parts, denoted as solvent A and solvent B; the zinc-based semiconductor photocatalyst modified with phenolic organic compounds is ground into powder to obtain zinc-based semiconductor powder modified with phenolic organic compounds; then the zinc-based semiconductor powder modified with phenolic organic compounds is added to solvent A, stirred and then ultrasonically treated to obtain a uniform mixture A. 2) Grind the prescribed amount of film-forming material into powder to obtain film-forming material powder; then add the film-forming material powder to solvent B and stir evenly to obtain mixture B; 3) Add the mixture A obtained in step 1) to the mixture B obtained in step 2), stir well, and obtain mixture C; 4) Add the prescribed amount of moisturizer to the mixture C obtained in step 3), and then perform ultrasonic treatment under stirring conditions to form a uniform and stable solution, which is the liquid bandage. 5) Fill the liquid bandage obtained in step 4) into a spray bottle or other storage container and seal it to obtain the finished product.
9. The method for preparing the photocatalytic hydrogen peroxide-producing liquid bandage according to claim 8, characterized in that, In step 1): the volume ratio of solvent A to solvent B is 1:1; the stirring time is 20-30 min; the ultrasonic treatment conditions are: power 300-1000 watts, time 3-30 minutes; In step 2): the stirring time is 20-30 minutes; In step 4), the ultrasonic conditions are: power 300-1000 watts, time 3-30 minutes.