Liquid band-aid capable of producing hydrogen peroxide through photocatalysis and preparation method of liquid band-aid

By using zinc-based semiconductor photocatalyst modified by phenolic organics and film-forming materials in liquid bandages, combined with hyaluronic acid moisturizers, photocatalytic generation of hydrogen peroxide is achieved, solving the problem of unsatisfactory sterilization effect of existing liquid bandages, and having good antibacterial and bactericidal effect and long-term use stability.

CN119971128AActive Publication Date: 2025-05-13JIANGSU UNIV
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Patent Information

Application Number
CN202510203468.9
Authority / Receiving Office
CN · China
Patent Type
Applications(China)
Current Assignee / Owner
Filing Date
2025-02-24
Publication Date
2025-05-13
Estimated Expiration
2045-02-24

AI Technical Summary

Technical Problem

Existing liquid bandages have problems such as strong irritation, poor sterilization effect, and may cause allergic reactions and toxic side effects to the human body.

Method used

A zinc-based semiconductor photocatalyst modified with phenolic organics, a film-forming material of chitosan hydrochloride and nitrocellulose, and a moisturizing agent of hyaluronic acid are used to generate hydrogen peroxide under light through photocatalytic reactions, thereby achieving antibacterial and bactericidal effect.

Benefits of technology

It has achieved hydrogen peroxide production under light, which has good antibacterial and bactericidal effect, and has long stability in use and good continuous bactericidal performance.

✦ Generated by Eureka AI based on patent content.

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Abstract

The invention belongs to the technical field of medical dressings, and particularly relates to a liquid band-aid capable of producing hydrogen peroxide through photocatalysis and a preparation method of the liquid band-aid. The liquid band-aid comprises the following components in percentage by weight: 0.1 to 5 percent of a zinc-based semiconductor photocatalyst modified by a phenolic organic matter, 2 to 10 percent of a film-forming material, 0.1 to 3 percent of a humectant and 82 to 97.8 percent of a mixed volatile solvent. The liquid band-aid is not limited by the shape and size of an injured wound and is suitable for various wounds on the superficial layer of the human body; under the illumination condition, hydrogen peroxide can be continuously and stably generated, meanwhile, different amounts of hydrogen peroxide can be applied according to the severity of a wound, and the yield of hydrogen peroxide is automatically adjusted; the long-time use stability is realized, so that the long-time efficient antibacterial and bactericidal effects are realized; the novel band-aid shows extremely wide application prospects due to excellent functionality and wide applicability, and is an important breakthrough and innovation of a medical dressing technology.
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Description

Technical Field

[0001] The invention belongs to the technical field of medical dressings, and specifically discloses a liquid bandage capable of producing hydrogen peroxide by photocatalysis and a preparation method thereof. Background Art

[0002] Band-Aids are widely used medical products in daily life, mainly used to protect wounds and promote healing. However, traditional Band-Aids are usually composed of dressings, adhesive tape and isolation paper, and have obvious limitations: 1) The disinfection effect is limited and it is difficult to provide continuous antibacterial protection; 2) The shape and size are fixed and cannot effectively cover large areas or irregular wounds; 3) The air permeability is poor, which is not conducive to wound healing; 4) It is disposable and not environmentally friendly.

[0003] In order to solve the shortcomings of traditional Band-Aids, many pharmaceutical companies and research institutions have developed liquid Band-Aids. Liquid Band-Aids are not restricted by the shape of the wound and can be directly applied or sprayed on the wound surface to form a protective film. They can also carry different active ingredients, are waterproof and breathable, and solve the problems of skin redness, swelling and discomfort caused by traditional Band-Aid adhesive tapes. For this reason, liquid Band-Aids have also become a hot topic in research.

[0004] However, some liquid bandages currently available and in patents still have problems such as large irritating odor and unsatisfactory bactericidal effect. For example, patent CN116271205A is a liquid bandage containing black phosphorus nanosheets and its preparation method, which includes film-forming substances, solvents, adhesion promoters, local anesthetics, antibacterial agents, anti-inflammatory agents, moisturizers and fragrances, wherein the antibacterial agent is a mixture of black phosphorus nanosheets and benzalkonium chloride. Although the liquid bandage containing black phosphorus nanosheets is easy to use and forms a film quickly, antibacterial materials such as benzalkonium chloride must be used, which not only causes allergic reactions, but also produces toxic and side effects on the human body. Patent CN110124095A is an antibacterial liquid bandage and its preparation method, and the antibacterial liquid bandage includes doxycycline, nitrocellulose, bletilla striata extract, plasticizer, liquid solvent and preservative. The doxycycline added to the liquid bandage is used as an antibacterial agent, and the amount used is large but the effective action time is short.

[0005] Therefore, developing a new type of highly efficient, environmentally friendly, and long-lasting Band-Aid is an important issue that needs to be addressed urgently. Summary of the invention

[0006] In view of the deficiencies in the prior art, the purpose of the present application is to provide a gel band-aid that produces hydrogen peroxide through photocatalysis and a method for preparing the same; by selecting specific materials and combining the corresponding preparation method, a gel band-aid that produces hydrogen peroxide through photocatalysis is obtained, which not only has the effects of antibacterial and sterilization and promoting wound healing, but also can enhance the wound care effect, improve the user experience, and solve the technical problems existing in the existing band-aids.

[0007] In one aspect of the present invention, a liquid bandage for photocatalytically producing hydrogen peroxide is provided, the components of which include 0.1 to 5 wt% of a zinc-based semiconductor photocatalyst modified with a phenolic organic compound, 2 to 10 wt% of a film-forming material, 0.1 to 3 wt% of a moisturizing agent, and 82 to 97.8 wt% of a mixed volatile solvent;

[0008] The film-forming material is a mixture of chitosan hydrochloride and cellulose nitrate;

[0009] The moisturizing agent is hyaluronic acid;

[0010] The volatile solvent is a mixture of ethanol and physiological saline.

[0011] The phenolic organic modified zinc-based semiconductor photocatalyst is a photocatalyst capable of producing hydrogen peroxide, including but not limited to: phenol-modified nitrogen-doped zinc oxide, phenol-modified zinc oxide, phenol-modified ZnO / ZnO 2 Composites, phenol-modified zinc single atom anchored carbon nitride and phenol-modified zinc sulfide, o-methoxyphenol-modified nitrogen-doped zinc oxide, o-methoxyphenol-modified zinc oxide containing oxygen defects, o-methoxyphenol-modified ZnO / ZnO 2 Composite, one or more of p-methoxyphenol-modified nitrogen-doped zinc oxide.

[0012] Furthermore, the mass ratio of chitosan hydrochloride to cellulose nitrate in the film-forming material is (1-2):(1-3). Furthermore, the mass ratio of chitosan hydrochloride to cellulose nitrate in the film-forming material is 1:1.5-2.

[0013] Furthermore, the volume ratio of ethanol to saline in the volatile solvent is (1-3):(1-8). Furthermore, the volume ratio of ethanol to saline in the volatile solvent is 1:1.

[0014] Furthermore, the moisturizing agent is hyaluronic acid with a molecular weight of 800,000 to 2,200,000 Daltons.

[0015] Furthermore, the zinc-based semiconductor photocatalyst modified by phenolic organic matter is preferably nitrogen-doped zinc oxide modified by o-methoxyphenol.

[0016] Furthermore, the preparation method of the o-methoxyphenol-modified nitrogen-doped zinc oxide comprises the following steps:

[0017] 1) Preparation of nitrogen-doped zinc oxide

[0018] Adding thiourea, anhydrous zinc acetate and ethylenediaminetetraacetic acid to deionized water in sequence, stirring evenly to obtain a mixed solution, and transferring the mixed solution to a reactor for hydrothermal reaction; after the reaction is completed, centrifuging, washing and drying to obtain a nitrogen-doped zinc oxide precursor; then calcining the nitrogen-doped zinc oxide precursor to obtain nitrogen-doped zinc oxide;

[0019] 2) O-methoxyphenol-modified nitrogen-doped zinc oxide

[0020] The ethanol is stirred under water bath conditions, and the nitrogen-doped zinc oxide obtained in step 1) is added while stirring to obtain a uniform suspension; then o-methoxyphenol is added dropwise to the above suspension, and the water bath conditions are maintained until the liquid evaporates completely to obtain o-methoxyphenol-modified nitrogen-doped zinc oxide.

[0021] In step 1) of the present invention:

[0022] The mass 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°C, and the hydrothermal reaction time is 6-12 hours;

[0025] The calcination temperature is 380 to 950° C., and the calcination time is 1 to 12 hours.

[0026] In step 2) of the present invention:

[0027] The temperature of the water bath is 40-45°C;

[0028] The mass ratio of nitrogen-doped zinc oxide to ethanol is 1:10-100;

[0029] The mass ratio of o-methoxyphenol to nitrogen-doped zinc oxide is 1:5-30.

[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, which are recorded as solvent A and solvent B; and the prescribed amount of phenolic organic modified zinc-based semiconductor photocatalyst is ground into powder to obtain phenolic organic modified zinc-based semiconductor powder; then the phenolic organic modified zinc-based semiconductor powder is added to solvent A, stirred and then ultrasonically treated to obtain a uniform mixed solution A;

[0032] 2) grinding the prescribed amount of film-forming material into powder to obtain film-forming material powder; then adding the film-forming material powder into solvent B, stirring evenly, to obtain mixed solution B;

[0033] 3) Pour the mixed solution A obtained in step 1) into the mixed solution B obtained in step 2), and stir evenly to obtain a mixed solution C;

[0034] 4) adding a prescribed amount of moisturizer to the mixed solution C obtained in step 3), and performing ultrasonic treatment under stirring to form a uniform and stable solution, i.e., a liquid band-aid;

[0035] 5) filling the liquid adhesive bandage obtained in step 4) into a spray bottle or other storage container and sealing the container to obtain a finished product.

[0036] In step 1) of the present 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 20-30min;

[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 preparation method of the liquid wound dressing of the present invention is simple, the finished product can be carried around, and it is simple and convenient to use.

[0045] 2. After the liquid band-aid prepared by the present invention is applied to the wound surface, it can catalyze air and wound tissue fluid to generate hydrogen peroxide under light irradiation, thereby achieving the effect of antibacterial and sterilization.

[0046] 3. The liquid wound prepared by the present 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 the present invention has long-term use stability, a long effective action time, and a continuous bactericidal performance within 24 hours. BRIEF DESCRIPTION OF THE DRAWINGS

[0048] Figure 1 This is a scanning electron microscope image of the nitrogen-doped zinc oxide modified with o-methoxyphenol prepared in Example 1.

[0049] Figure 2 This is the scanning X-ray electron diffraction pattern of the nitrogen-doped zinc oxide modified with o-methoxyphenol prepared in Example 1.

[0050] Figure 3 This is an optical microscope photograph of the phenol-modified nitrogen-doped zinc oxide described in Example 2.

[0051] Figure 4 This is a performance diagram of the photocatalytic production of hydrogen peroxide by the liquid Band-Aid in Example 13.

[0052] Figure 5 This is a performance diagram of the photocatalytic production of hydrogen peroxide by the liquid Band-Aid in Example 14.

[0053] Figure 6 1 is a performance graph of the antibacterial and bactericidal efficacy of the liquid band-aid in Example 15; wherein Figure A is the growth of Escherichia coli in the experimental group; and Figure B is the growth of Escherichia coli in the control group. DETAILED DESCRIPTION

[0054] The present invention is further described below in conjunction with the accompanying drawings and specific implementation methods, but the protection scope of the present invention is not limited thereto.

[0055] The present invention is described in detail below by specific examples. It must be pointed out that these examples are used to illustrate the present invention, rather than to limit the present invention. The reagents or materials mentioned in the present invention can be prepared by conventional methods or purchased from the market unless otherwise specified.

[0056] Example 1: Preparation of o-methoxyphenol-modified nitrogen-doped zinc oxide

[0057] 1) 7.612 mg of thiourea, 18.347 mg of anhydrous zinc acetate and 1.5 mg of ethylenediaminetetraacetic acid were slowly added to a 500 mL beaker containing 300 mL of deionized water in sequence, and after stirring evenly, the mixed solution in the beaker was transferred to a reactor for hydrothermal reaction at a temperature of 160° C. After reacting for 8 hours, the reactor was naturally cooled to room temperature; the mixture in the reactor was centrifuged (10000 r / min, 15 min), and the lower layer of the precipitate in the centrifuge tube was collected; then the solid precipitate was washed with deionized water and ethanol for 3 times respectively; the washed solid precipitate was dried in a vacuum oven at 50° C. for 24 hours to obtain a nitrogen-doped zinc oxide precursor; then the nitrogen-doped zinc oxide precursor was calcined in a muffle furnace at 500° C. for 2 hours to obtain nitrogen-doped zinc oxide.

[0058] 2) 100 mL of ethanol was slowly added to a 250 mL round-bottom flask, which was then placed in a 40° C. water bath, and 2 g of the nitrogen-doped zinc oxide obtained in step 1) was slowly added while stirring to obtain a uniform suspension; 0.2 mg of o-methoxyphenol was then slowly added dropwise to the suspension, and a 40° C. water bath was maintained until the liquid in the flask evaporated completely, and the obtained solid product was o-methoxyphenol-modified nitrogen-doped zinc oxide. Figure 1 is a scanning electron micrograph of the prepared o-methoxyphenol-modified nitrogen-doped zinc oxide; Figure 2 is a scanning X-ray electron diffraction pattern of the prepared o-methoxyphenol-modified nitrogen-doped zinc oxide.

[0059] Example 2: Preparation of phenol-modified nitrogen-doped zinc oxide

[0060] In this example, o-methoxyphenol was replaced with an equal amount of phenol, and the remaining steps were the same as in Example 1, and finally phenol-modified nitrogen-doped zinc oxide was obtained. Figure 3 is an optical micrograph of phenol-modified nitrogen-doped zinc oxide.

[0061] Example 3: Preparation of the liquid wound dressing of the present invention

[0062] 1. The components of the liquid wound dressing include (the total amount is 100wt%):

[0063] 5.0wt% of phenolic organic modified zinc-based semiconductor photocatalyst (nitrogen-doped zinc oxide modified by o-methoxyphenol), 5.0wt% of film-forming material (chitosan hydrochloride and cellulose nitrate in a mass ratio of 1:2), 1.0wt% of moisturizing agent (hyaluronic acid of 1000000-2000000 Daltons), 89.0wt% of mixed volatile solvent (ethanol and saline mixed in equal volumes);

[0064] 2. Preparation method:

[0065] Select the dosage according to the distribution ratio of each group in the liquid bandage, and divide the mixed volatile solvent into 2 parts, recorded as solvent A and solvent B; perform the following operations:

[0066] 1) grinding the nitrogen-doped zinc oxide modified by o-methoxyphenol into powder to obtain nitrogen-doped zinc oxide powder modified by o-methoxyphenol; then adding the nitrogen-doped zinc oxide powder modified by o-methoxyphenol into solvent A, stirring for 30 minutes, and then ultrasonicating at 500 watts for 10 minutes to obtain a uniform mixed solution;

[0067] 2) mixing chitosan hydrochloride and nitrocellulose in a mass ratio of 1:2 and grinding them into powder to obtain a mixed powder of chitosan hydrochloride and nitrocellulose; then adding the mixed powder of chitosan hydrochloride and nitrocellulose to solvent B, stirring for 30 minutes, and obtaining a uniform mixed solution;

[0068] 3) slowly pouring the mixed solution obtained in step 1) into the mixed solution obtained in step 2), and stirring for 30 minutes to obtain a uniform mixed solution;

[0069] 4) Finally, hyaluronic acid is slowly added to the mixed solution obtained in step 3), and the mixture is continuously stirred and ultrasonically treated for 10 minutes (power 500 watts) to form a uniform and stable liquid bandage;

[0070] 5) Filling the liquid adhesive bandage obtained in step (4) into a spray bottle or other suitable storage container and sealing the container to obtain a finished product.

[0071] Embodiment 4:

[0072] Same as Example 3, except that the components are as follows:

[0073] The liquid wound dressing comprises: 0.1wt% of a zinc-based semiconductor photocatalyst modified with phenolic organic matter (nitrogen-doped zinc oxide modified with o-methoxyphenol), 10wt% of a film-forming material (chitosan hydrochloride and cellulose nitrate in a mass ratio of 1:2), 3wt% of a moisturizer (800,000 to 1,200,000 Daltons of hyaluronic acid) and 86.9wt% of a mixed volatile solvent (ethanol and saline mixed in equal volumes).

[0074] Embodiment 5:

[0075] Same as Example 3, except that the components are as follows:

[0076] The liquid wound dressing comprises: 5wt% of a zinc-based semiconductor photocatalyst modified with phenolic organic matter (nitrogen-doped zinc oxide modified with o-methoxyphenol), 6wt% of a film-forming material (chitosan hydrochloride and cellulose nitrate in a mass ratio of 1:2), 0.1wt% of a moisturizer (hyaluronic acid of 1,000,000 to 1,800,000 Daltons) and 88.9wt% of a mixed volatile solvent (ethanol and saline mixed in equal volumes).

[0077] Embodiment 6:

[0078] Same as Example 3, except that the components are as follows:

[0079] The liquid wound dressing comprises: 2.5wt% of a zinc-based semiconductor photocatalyst modified with phenolic organic matter (nitrogen-doped zinc oxide modified with o-methoxyphenol), 2wt% of a film-forming material (chitosan hydrochloride and cellulose nitrate in a mass ratio of 1:2), 2wt% of a moisturizer (1000000-2000000 Dalton hyaluronic acid) and 93.5wt% of a mixed volatile solvent (ethanol and saline mixed in equal volumes).

[0080] Embodiment 7:

[0081] Same as Example 3, except that the components are as follows:

[0082] The liquid wound dressing comprises: 3wt% of a zinc-based semiconductor photocatalyst modified with phenolic organic matter (phenol-modified nitrogen-doped zinc oxide), 2wt% of a film-forming material (chitosan hydrochloride and cellulose nitrate in a mass ratio of 1:2), 2wt% of a moisturizer (800,000 to 2,200,000 Daltons of hyaluronic acid) and 93wt% of a mixed volatile solvent (ethanol and saline mixed in a volume ratio of 1:2).

[0083] Embodiment 8:

[0084] Same as Example 3, except that the components are as follows:

[0085] The liquid wound dressing comprises: 2.5wt% of a zinc-based semiconductor photocatalyst modified with phenolic organic matter (nitrogen-doped zinc oxide modified with p-methoxyphenol), 3wt% of a film-forming material (chitosan hydrochloride and cellulose nitrate in a mass ratio of 1:2), 1.3wt% of a moisturizing agent (800,000 to 2,000,000 Daltons of hyaluronic acid) and 93.2wt% of a mixed volatile solvent (ethanol and saline mixed 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 that in Example 1, except that o-methoxyphenol is replaced by an equal amount of p-methoxyphenol.

[0086] Embodiment 9:

[0087] Same as Example 3, except that the components are as follows:

[0088] The liquid wound dressing comprises: 2.5wt% of a zinc-based semiconductor photocatalyst modified with phenolic organic matter (a combination of nitrogen-doped zinc oxide modified with o-methoxyphenol and zinc oxide containing oxygen defects modified with o-methoxyphenol in a mass fraction of 1:1), 9wt% of a film-forming material (chitosan hydrochloride and cellulose nitrate in a mass ratio of 1:2), 2.5wt% of a moisturizer (hyaluronic acid of 1,000,000 to 2,000,000 Daltons) and 86wt% of a mixed volatile solvent (ethanol and saline mixed in a volume ratio of 3:1).

[0089] The preparation method of the zinc oxide containing oxygen defects modified by o-methoxyphenol is as follows: 0.1M zinc nitrate hexahydrate (Zn(NO 3 ) 2 6H 2 O) was dissolved in 100 mL of deionized water and stirred until completely dissolved. Under stirring, 0.1 M sodium borohydride (NaBH 4 ) solution until the solution becomes transparent, and heat the mixed solution at 80°C for 2 hours to promote the formation of oxygen defects. The generated precipitate is collected by vacuum filtration and washed several times with deionized water to remove residual reactants. The washed precipitate is dried at 60°C for 12 hours to obtain zinc oxide powder containing oxygen defects. The dried zinc oxide powder is dispersed in 100mL of ethanol, and o-methoxyphenol (equal amount of substance) 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°C for 12 hours to obtain o-methoxyphenol-modified zinc oxide containing oxygen defects.

[0090] Embodiment 10:

[0091] Same as Example 3, except that the components are as follows:

[0092] The liquid wound dressing comprises: 1.5 wt% of a zinc-based semiconductor photocatalyst modified with phenolic organic matter (phenol-modified ZnO / ZnO 2 The invention discloses a method for preparing a novel nanostructured carbon nanotube film comprising: a nanostructured carbon nanotube film and an o-methoxyphenol-modified zinc oxide containing oxygen defects in a mass fraction of 2:1), 6wt% of a film-forming material (chitosan hydrochloride and cellulose nitrate in a mass ratio of 1:2), 2.5wt% of a moisturizing agent (800,000 to 2,200,000 daltons of hyaluronic acid) and 90wt% of a mixed volatile solvent (ethanol and saline mixed in a volume ratio of 3:1); wherein the phenol modification method is the same as that in Example 1, the main difference being that the modifier is replaced by an equal amount of phenol instead of o-methoxyphenol; the preparation of the o-methoxyphenol-modified zinc oxide containing oxygen defects is the same as that in Example 9.

[0093] Embodiment 11:

[0094] Same as Example 3, except that the components are as follows:

[0095] The components of the liquid wound dressing include: 1wt% of a zinc-based semiconductor photocatalyst modified with phenolic organic matter (a combination of nitrogen-doped zinc oxide modified with o-methoxyphenol and nitrogen-doped zinc oxide modified with p-methoxyphenol in a mass fraction of 1:3), 8.5wt% of a film-forming material (chitosan hydrochloride and cellulose nitrate in a mass ratio of 1:2), 2.5wt% of a moisturizer (800,000 to 1,000,000 Daltons of hyaluronic acid) and 88wt% of a mixed volatile solvent (ethanol and saline mixed in a volume ratio of 3:1); the preparation of nitrogen-doped zinc oxide modified with p-methoxyphenol is the same as that in Example 8.

[0096] Embodiment 12:

[0097] Same as Example 3, except that the components are as follows:

[0098] The liquid wound dressing comprises: 2.5wt% of a zinc-based semiconductor photocatalyst modified with phenolic organic matter (a combination of nitrogen-doped zinc oxide modified with o-methoxyphenol and nitrogen-doped zinc oxide modified with phenol in a mass fraction of 1:3), 5wt% of a film-forming material (chitosan hydrochloride and cellulose nitrate in a mass ratio of 1:2), 1.2wt% of a moisturizer (800000-2200000 Dalton hyaluronic acid) and 91.3wt% of a mixed volatile solvent (ethanol and saline mixed in equal volumes).

[0099] Example 13: Study on the photocatalytic hydrogen peroxide production performance of the liquid bandage of the present invention

[0100] 1) 100 μL of the liquid bandage prepared in Example 3 was sprayed on a glass sheet with a width of 1 cm and a length of 2 cm. After natural drying for 24 hours, the film on the glass sheet was peeled off.

[0101] 2) The film peeled off in step 1) was added into a 50 mL beaker containing 20 mL of deionized water, stirred for 30 minutes, and then the beaker was placed under LED light with a wavelength of 405 nm for 3 hours.

[0102] 3) Detect the concentration of generated hydrogen peroxide.

[0103] The results are as follows Figure 4 As shown, under the irradiation condition of 405nm LED light, the concentration of hydrogen peroxide gradually increases with the increase of light irradiation time, and the linear relationship is good; and after 3 hours, the concentration of generated hydrogen peroxide is already higher than 300mol / L; indicating that the prepared liquid Band-Aid can effectively generate hydrogen peroxide under light.

[0104] Example 14: Study on the photocatalytic hydrogen peroxide production performance of the liquid bandage of the present invention

[0105] 1) 100 μL of the liquid adhesive bandage prepared in Examples 4-12 was sprayed on glass sheets with a width of 1 cm and a length of 2 cm, respectively. After natural drying for 24 hours, the film on the glass sheet was peeled off.

[0106] 2) The films peeled off in step 1) were added into a 50 mL beaker containing 20 mL of deionized water, stirred for 30 minutes, and then the beaker was placed under LED light with a wavelength of 405 nm for 3 hours.

[0107] 3) Detect the concentration of generated hydrogen peroxide.

[0108] The results are as follows Figure 5 As shown, after irradiation with 405nm LED light for 3 hours, the concentration of generated hydrogen peroxide was higher than 180mol / L, indicating that the prepared liquid band-aid can generate hydrogen peroxide under light, and the effect is significant.

[0109] Example 15: Study on the bactericidal and antibacterial effects of the liquid bandage of the present invention (taking Example 3 as an example)

[0110] 1) Apply 100 μL of the liquid bandage prepared in Example 3 on the surface of the agar plate;

[0111] 2) Spread 100 μL of E. coli solution on 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 culture at 37°C for 24 hours, observe the growth of E. coli in the culture dish, and record and take photos.

[0113] Comparative Example:

[0114] 1) Apply 100 μL of solvent on the surface of the agar plate, where the solvent is a mixture of ethanol and saline in a volume ratio of 1:1;

[0115] 2) Spread 100 μL of E. coli solution on 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 culture at 37°C for 24 hours, observe the growth of E. coli in the culture dish, and record and take photos.

[0117] Note: Agar plates were sterilized by autoclaving at 121°C for 15 minutes before use.

[0118] The results are as follows Figure 6As shown, Figure A shows the growth of E. coli after applying the liquid bandage (experimental group); Figure B shows the growth of E. coli without applying the liquid bandage (control group). The results are obvious. While the control group is full of colonies, the experimental group treated with the liquid bandage of the present invention has no colony growth, indicating that the liquid bandage prepared by the present invention has a good antibacterial effect.

[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 this specification has described the present invention in detail with reference to the above embodiments, a person skilled in the art should understand that the present invention can still be modified or replaced by equivalents; and all technical solutions and improvements thereof that do not depart from the spirit and scope of the present invention should be included in the scope of the claims of the present invention.

Claims

1. A liquid bandage for photocatalytically producing hydrogen peroxide, characterized in that: The liquid bandage component comprises 0.1 to 5 wt% of a zinc-based semiconductor photocatalyst modified by a phenolic organic compound, 2 to 10 wt% of a film-forming material, 0.1 to 3 wt% of a moisturizing agent and 82 to 97.8 wt% of a mixed volatile solvent; The film-forming material is a mixture of chitosan hydrochloride and cellulose nitrate; The moisturizing agent is hyaluronic acid; The mixed volatile solvent is a mixture of ethanol and physiological saline; The zinc-based semiconductor photocatalyst modified by phenolic organic matter is a photocatalyst capable of producing hydrogen peroxide, including but not limited to: one or more of phenol-modified nitrogen-doped zinc oxide, phenol-modified zinc oxide, phenol-modified ZnO / ZnO2 complex, phenol-modified zinc single atom anchored carbon nitride, phenol-modified zinc sulfide, o-methoxyphenol-modified nitrogen-doped zinc oxide, o-methoxyphenol-modified zinc oxide containing oxygen defects, o-methoxyphenol-modified ZnO / ZnO2 complex, and p-methoxyphenol-modified nitrogen-doped zinc oxide.

2. The liquid bandage for photocatalytically producing hydrogen peroxide according to claim 1, characterized in that: The mass ratio of chitosan hydrochloride and cellulose nitrate in the film-forming material is (1-2):(1-3); the volume ratio of ethanol and physiological saline in the volatile solvent is (1-3):(1-8); the moisturizing agent is hyaluronic acid with a molecular weight of 800,000 to 2,200,000 Daltons; and the zinc-based semiconductor photocatalyst modified with phenolic organic matter is nitrogen-doped zinc oxide modified with o-methoxyphenol.

3. The liquid bandage for photocatalytically producing hydrogen peroxide according to claim 2, characterized in that: The mass ratio of chitosan hydrochloride to cellulose nitrate 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 photocatalytically producing hydrogen peroxide according to claim 1, characterized in that: The preparation method of the o-methoxyphenol-modified nitrogen-doped zinc oxide comprises the following steps: 1) Preparation of nitrogen-doped zinc oxide; Adding thiourea, anhydrous zinc acetate and ethylenediaminetetraacetic acid to deionized water in sequence, stirring evenly to obtain a mixed solution, and transferring the mixed solution to a reactor for hydrothermal reaction; after the reaction is completed, centrifuging, washing and drying to obtain a nitrogen-doped zinc oxide precursor; then calcining the nitrogen-doped zinc oxide precursor to obtain nitrogen-doped zinc oxide; 2) o-methoxyphenol-modified nitrogen-doped zinc oxide; The ethanol is stirred under water bath conditions, and the nitrogen-doped zinc oxide obtained in step 1) is added while stirring to obtain a uniform suspension; then o-methoxyphenol is added dropwise to the above suspension, and the water bath conditions are maintained until the liquid evaporates completely, and the obtained solid product is o-methoxyphenol-modified nitrogen-doped zinc oxide.

5. The liquid bandage for photocatalytically generating hydrogen peroxide according to claim 4, characterized in that: In step 1): The mass 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 to 300; The temperature of the hydrothermal reaction is 150 to 180° C., and the time of the hydrothermal reaction is 6 to 12 hours; The calcination temperature is 380 to 950° C., and the calcination time is 1 to 12 hours.

6. The liquid bandage for photocatalytically generating hydrogen peroxide according to claim 4, characterized in that: In step 2): The temperature of the water bath is 40-45°C; 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 photocatalytically generating hydrogen peroxide according to any one of claims 1 to 6, characterized in that: The liquid bandage can form a thin film after being applied on the wound surface.

8. The use of the liquid bandage for photocatalytically generating hydrogen peroxide according to claim 7 for achieving bacteriostasis and sterilization, characterized in that: The thin film formed by the liquid Band-Aid applied to the wound surface can catalyze the reaction of oxygen in the air and wound tissue fluid to produce hydrogen peroxide under light, thereby achieving the bactericidal and antibacterial effects on the wound and the area around the wound.

9. The method for preparing a liquid bandage for photocatalytically generating hydrogen peroxide according to any one of claims 1 to 6, characterized in that: Here are the steps: 1) First, the mixed volatile solvent is divided into two parts, which are recorded as solvent A and solvent B; and the prescribed amount of phenolic organic modified zinc-based semiconductor photocatalyst is ground into powder to obtain phenolic organic modified zinc-based semiconductor powder; then the phenolic organic modified zinc-based semiconductor powder is added to solvent A, stirred and then ultrasonically treated to obtain a uniform mixed solution A; 2) grinding the prescribed amount of film-forming material into powder to obtain film-forming material powder; then adding the film-forming material powder into solvent B, stirring evenly, to obtain mixed solution B; 3) adding the mixed solution A obtained in step 1) to the mixed solution B obtained in step 2), stirring evenly to obtain a mixed solution C; 4) adding a prescribed amount of moisturizer to the mixed solution C obtained in step 3), and performing ultrasonic treatment under stirring to form a uniform and stable solution, i.e., a liquid band-aid; 5) filling the liquid adhesive bandage obtained in step 4) into a spray bottle or other storage container and sealing the container to obtain a finished product.

10. The method for preparing a liquid bandage for photocatalytic hydrogen peroxide production according to claim 9, characterized in that: In step 1), the volume ratio of solvent A to solvent B is 1:1; the stirring time is 20-30 minutes; 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.

Citation Information

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