A tooth whitening catalytic material based on photothermal integrated Fenton reaction and its preparation method and application

Abstract

The present invention relates to a tooth-whitening catalytic material based on a photothermal integrated Fenton reaction, as well as its preparation method and application. The present invention utilizes an iron-doped carbon aerogel with a large specific surface area, high conductivity, and strong adsorption as a substrate, and modified TiO2 nanoparticles as the primary component of the tooth-whitening product. Laser light of a specific wavelength excites the material's photothermal Fenton effect, releasing a large amount of active substances, thereby degrading tooth surface pigments and achieving the purpose of tooth whitening. Compared with existing technologies, the present invention has the advantage of reducing the adverse effects of high-concentration hydrogen peroxide while not damaging normal oral soft tissue, achieving efficient and safe bleaching results in a short period of time.

Description

Technical Field

[0001] The present invention belongs to the technical field of tooth whitening, and specifically relates to a tooth whitening catalytic material based on a photothermal integrated Fenton reaction, and a preparation method and application thereof. Background Art

[0002] Oral diseases are a constant companion and a major scourge plaguing humanity. Oral health is not only a crucial pillar of physical well-being but also a key factor in the balance of the human body. As society continues to progress, people's pursuit of oral health is growing. Simultaneously, with evolving aesthetic standards, tooth whitening has become a crucial tool for enhancing self-confidence and appeal. Surveys show that over 80% of people believe that tooth whitening improves their image and social skills. However, due to neglected oral care and interventions, problems such as tooth decay and tooth staining have become rampant, affecting patients of all ages. More seriously, oral diseases can lead to various complications and compromise overall health. Therefore, strengthening oral care and preventive measures are essential for maintaining overall health and improving quality of life. Therefore, finding a method that effectively decomposes various pigments on the tooth surface is a key area of ​​modern tooth whitening technology. Developing safe and effective tooth whitening functional materials and related products will help meet the whitening needs of a broad population.

[0003] The tooth bleaching mechanism is based on the oxidative degradation of pigments by hydrogen peroxide molecules and reactive oxygen species derived from hydrogen peroxide (mainly ·OH), and ·OH (2.80eV) has a stronger redox potential than hydrogen peroxide (1.78eV). Therefore, a promising strategy to improve the bleaching ability of low-concentration hydrogen peroxide is to generate high concentrations of ·OH. Fenton catalysts have the inherent property of converting hydrogen peroxide into ·OH, and have outstanding advantages in tooth bleaching applications such as high efficiency, mild reaction conditions, and simple operating procedures. However, existing tooth whitening materials using the Fenton reaction have a weak ability to catalyze hydrogen peroxide to produce ·OH, resulting in poor whitening effects. The frequency and duration of use are too long, which is not conducive to their promotion and application. Summary of the Invention

[0004] The purpose of the present invention is to overcome the defects of the above-mentioned prior art and provide a safe, controllable, efficient and stable tooth whitening effect tooth whitening catalytic material based on photothermal integrated Fenton reaction and its preparation method and application.

[0005] The purpose of the present invention can be achieved by the following technical solutions:

[0006] One of the present inventions provides a method for preparing a tooth whitening catalytic material based on a photothermal integrated Fenton reaction, comprising the following steps:

[0007] S1: Mix resorcinol, formaldehyde, and sodium carbonate in a mass ratio of (5 - 7):(8 - 10):(0.01 - 0.02) to obtain a precursor solution of the aerogel material. Before adding sodium carbonate, dissolve it in deionized water with a concentration range of 3 - 4 g / L.

[0008] S2: Add iron phthalocyanine powder to the above precursor solution to 0.1 - 3 wt%, and cause a phenolic aldehyde condensation reaction to form a metal - organic wet gel.

[0009] S3: Replace the water in the above metal - organic wet gel with an acetone solution to obtain an organic aerogel.

[0010] S4: Carbonize the above organic aerogel under an inert gas atmosphere to obtain an iron - doped carbon aerogel material.

[0011] S5: Modify TiO₂ using the NaBH₄ solid - state chemical reduction method. Grind the mixture of TiO₂ and NaBH₄ and then perform vacuum calcination treatment to obtain TiO 2-x nanoparticles.

[0012] S6: Mix the above iron - doped carbon aerogel material with the modified TiO 2-x nanoparticles to obtain the tooth - whitening catalytic material, specifically a titanium dioxide - supported composite iron - doped carbon aerogel catalytic material.

[0013] Further, the mixing in step S1 is specifically: while stirring, gradually dropwise add an aqueous formaldehyde solution and an aqueous sodium carbonate solution to an aqueous resorcinol solution. Preferably, add 87 mL of an aqueous formaldehyde solution and 12 mL of an aqueous sodium carbonate solution with a concentration of 4.2 g / L.

[0014] Further, the reaction conditions for the phenolic aldehyde condensation reaction in step S2 are: first react at 30 °C for 22 - 26 h, preferably 24 h, then immediately react at 50 °C for 22 - 26 h, preferably 24 h, and finally react at 90 °C for 70 - 74 h, preferably 72 h.

[0015] Further, the replacement in step S3 is specifically to soak the metal - organic wet gel in an acetone solution for 70 - 74 h, preferably 72 h, and replace the acetone solution every 22 - 26 h. After soaking, the aerogel is naturally dried, and a yellow -块状 organic carbon aerogel can be obtained after the acetone has completely evaporated.

[0016] Further, the inert gas in step S4 is selected from one or more of N₂, Ar, or He, and the carbonization is specifically to hold at 950 °C for 4 h.

[0017] Further, for the TiO 2-x nanoparticles in step S5, 0 < x < 1, and 2 - x represents having oxygen vacancies.

[0018] Furthermore, the TiO2 in step S5 is preferably P25 TiO2, the mass ratio of TiO2 to NaBH4 is 4:3, and 0.5 mL of distilled water is added for every 3.5 g of the mixture during the grinding process.

[0019] Furthermore, the mixing method in step S6 is one or more of stirring mixing, grinding or sieving mixing.

[0020] The second aspect of the present invention provides a carbon aerogel catalytic material prepared according to the above-mentioned method for preparing a tooth whitening catalytic material based on the integrated photothermal Fenton reaction.

[0021] The third aspect of the present invention provides the use of the above-mentioned carbon aerogel catalytic material in tooth whitening products.

[0022] The teeth whitening application described in the present invention can bring a teeth whitening product containing a titanium dioxide-loaded composite iron-doped carbon aerogel catalytic material with integrated photothermal function into contact with teeth, and then irradiate with a teeth whitening device containing blue light with a wavelength of 450-480nm to stimulate the photocatalytic effect of the material to produce hydroxyl free radicals, which degrade organic matter and pigments on the tooth surface, thereby achieving a teeth whitening effect.

[0023] Compared with the prior art, the present invention has the following advantages:

[0024] (1) The present invention uses iron-doped carbon aerogel with large specific surface area, high conductivity and strong adsorption as the substrate, and modified TiO2 nanoparticles as the main component of the tooth whitening product. Through a laser of a specific wavelength, the photothermal Fenton effect of the material is stimulated to release a large amount of active substances, thereby degrading the pigment on the tooth surface and achieving the purpose of tooth whitening.

[0025] (2) The present invention reduces the amount of hydrogen peroxide used in the tooth bleaching process without damaging normal oral soft tissue. It can achieve efficient and safe bleaching results in a short period of time, and is expected to be similar to commercial bleaching methods. The method is simple to operate and easy to use, making it a daily teeth whitening product suitable for home use.

[0026] (3) The present invention can be applied to products containing tooth whitening catalytic materials, including toothpaste, tooth strips, gels, etc., as well as medical braces, special toothbrushes, and teeth whitening devices containing the material. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] Figure 1 This is the methyl orange degradation result of the titanium dioxide-supported composite iron-doped carbon aerogel catalytic material under light environment in Example 2 of the present application;

[0028] Figure 2This is a schematic diagram of the effect of teeth after 1 hour of whitening treatment in Example 3 of the present application;

[0029] Figure 3 This is a SEM photograph of the tooth surface after 1 hour of whitening treatment in Example 4 of the present application;

[0030] Figure 4 This is a SEM photograph of the tooth surface after treatment with 30% hydrogen peroxide for 1 hour in Example 4 of the present application. DETAILED DESCRIPTION

[0031] The following description sets forth numerous specific details to facilitate a thorough understanding of the present invention. However, the present invention can be implemented in many other ways than those described herein, and those skilled in the art may make similar modifications without departing from the scope of the present invention. Therefore, the present invention is not limited to the specific implementations disclosed below.

[0032] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those commonly understood by those skilled in the art of the present invention. The terms used in this specification of the present invention are only for the purpose of describing specific embodiments and are not intended to limit the present invention.

[0033] Example 1

[0034] The preparation method of a tooth whitening catalytic material based on a photothermal integrated Fenton reaction comprises the following steps:

[0035] 1) First, 66.0 g of resorcinol was added to 115.8 mL of deionized water and stirred until completely dissolved. Then, 87 mL of formaldehyde aqueous solution and 12 mL of 4.2 g / L sodium carbonate solution were added dropwise while stirring. After being thoroughly stirred, a precursor solution was obtained.

[0036] 2) Subsequently, iron phthalocyanine powder was added to the precursor solution to a concentration of 2 wt %. After uniform mixing, the mixture was poured into a rectangular glass container of a specified size and sealed. The reaction container was then placed in an electrically heated constant-temperature forced air drying oven at 30°C, 50°C, and 90°C for 24 hours, 24 hours, and 72 hours, respectively, to allow the precursor solution to undergo a phenolic polycondensation reaction to form a metal organic wet gel.

[0037] 3) The resulting wet metal-organic gel was immersed in an acetone solution at room temperature for 72 hours, with the acetone solution replaced every 24 hours to completely displace the water in the wet metal-organic gel. The aerogel was then allowed to dry naturally. Once the acetone had completely evaporated, a yellow block of organic carbon aerogel was obtained.

[0038] 4) The prepared block organic aerogel was placed in the center of a tubular furnace. In an N2 atmosphere with a flow rate of 200 mL / min, the temperature of the tubular furnace was programmed to 950°C at a heating rate of 2.5°C / min, and kept at 950°C for 4 h. Finally, the temperature of the tubular furnace was lowered to room temperature at the same cooling rate, and FeNCA carbon aerogel material was obtained after grinding.

[0039] 5) Using P25 TiO2 as raw material, modified TiO was prepared by NaBH4 solid-state chemical reduction method. 2-x Nanoparticles. A mixture of TiO2 and NaBH4 with a mass ratio of 4:3 was ground for 30 minutes. 0.5 mL of distilled water was added to every 3.5 g of the mixture for further grinding. The resulting mixture was transferred to a porcelain boat, placed in a tube furnace, and heated to 365°C at a rate of 10°C / min under vacuum atmosphere and maintained for 45 minutes. After the reaction was completed, the naturally cooled sample was washed with deionized water and dried at 60°C for 8 hours to obtain modified TiO 2-x Nanoparticles.

[0040] 6) Iron-doped carbon aerogel material and modified TiO 2-x The nanoparticles are mixed to obtain the final catalytic material, namely titanium dioxide-supported composite iron-doped carbon aerogel catalytic material.

[0041] Example 2

[0042] The titanium dioxide-supported composite iron-doped carbon aerogel catalytic material was placed in a 20 mg / L methyl orange or Congo red solution, and the degradation efficiency change diagram after light treatment and photothermal integrated treatment was obtained ( Figure 1 ). Expected results: The degradation efficiency of the integrated photothermal treatment is significant. This example shows that the titanium dioxide-supported composite iron-doped carbon aerogel catalytic material has a significant pigment degradation effect under light environment. This example proves that the titanium dioxide-supported composite iron-doped carbon aerogel catalytic material used is feasible for achieving teeth whitening.

[0043] Example 3

[0044] In order to simulate the effect of the integrated photothermal Fenton effect on teeth whitening, the teeth that had been soaked in black tea solution for a week were taken out and rinsed, and then placed in a suspension of titanium dioxide-loaded composite iron-doped carbon aerogel catalytic material with a concentration of 1 mg / mL and 6% hydrogen peroxide for light treatment, that is, treatment with blue light with a wavelength of 450-480 nm. Figure 2 As shown in the figure, after 1 hour, the teeth became significantly whiter than before treatment; while the teeth that were not treated with titanium dioxide-loaded composite iron-doped carbon aerogel catalytic material and were only treated with hydrogen peroxide light did not change significantly in color, confirming the feasibility of titanium dioxide-loaded composite iron-doped carbon aerogel catalytic material.

[0045] Example 4

[0046] Enamel damage experiment. A titanium dioxide-loaded composite iron-doped carbon aerogel catalytic material dispersion with a concentration of 1 mg / mL and hydrogen peroxide with a concentration of 6% or 30% without the material were used to whiten teeth for 1 hour. After natural air drying, the teeth were sliced ​​and fixed, and a scanning electron microscope was used to observe whether the structure of the enamel surface had changed. Figure 3 、 Figure 4 As shown, the group without adding material ( Figure 4 ), after being treated with 30% hydrogen peroxide for 1 hour, the surface structure of the enamel was severely damaged, while after being treated with titanium dioxide-loaded composite iron-doped carbon aerogel catalytic material for 1 hour ( Figure 3 ), without causing obvious damage to the tooth surface structure, which is almost the same as the original tooth surface structure.

[0047] The above description of the embodiments is intended to facilitate understanding and use of the invention by those skilled in the art. It will be apparent that those skilled in the art can readily make various modifications to these embodiments and apply the general principles described herein to other embodiments without requiring inventive effort. Therefore, the present invention is not limited to the above-described embodiments. Improvements and modifications made by those skilled in the art based on the disclosure of the present invention, without departing from the scope of the present invention, should be within the scope of protection of the present invention.

Claims

1. A method for preparing a tooth whitening catalytic material based on photothermal integrated Fenton reaction, characterized in that: The following steps are involved: S1: resorcinol, formaldehyde and sodium carbonate are mixed in a mass ratio of (5-7): (8-10): (0.01-0.02) to obtain a precursor solution of an aerogel material, wherein the sodium carbonate is dissolved in deionized water before addition, and the concentration range is 3-4 g / L; S2: adding 0.1-3 wt% of iron phthalocyanine powder to the above precursor solution to cause a phenolic polycondensation reaction to form a metal organic wet gel; S3: using an acetone solution to displace the water in the metal organic wet gel to obtain an organic aerogel; S4: carbonizing the organic aerogel under an inert gas atmosphere to obtain an iron-doped carbon aerogel material; S5: Modification of TiO2 by NaBH4 solid-state chemical reduction method: Grind the mixture of TiO2 and NaBH4 and then calcine it in vacuum to obtain TiO 2-x Nanoparticles; S6: The above iron-doped carbon aerogel material is mixed with modified TiO 2-x The nanoparticles are mixed to obtain the teeth whitening catalytic material.

2. The method for preparing a tooth whitening catalytic material based on photothermal integrated Fenton reaction according to claim 1, characterized in that: The mixing in step S1 specifically comprises: adding the formaldehyde aqueous solution and the sodium carbonate solution dropwise to the resorcinol aqueous solution while stirring.

3. The method for preparing a tooth whitening catalytic material based on photothermal integrated Fenton reaction according to claim 1, characterized in that: The reaction conditions of the phenolic polycondensation reaction in step S2 are: first, react at 30°C for 22-26 h, then react at 50°C for 22-26 h, and finally react at 90°C for 70-74 h.

4. The method for preparing a tooth whitening catalytic material based on photothermal integrated Fenton reaction according to claim 1, characterized in that: The replacement described in step S3 is specifically to soak the metal organic wet gel in an acetone solution for 70-74 hours, and the acetone solution is replaced every 22-26 hours. The aerogel after soaking is naturally dried, and a yellow block organic carbon aerogel is obtained after the acetone is completely evaporated.

5. The method for preparing a tooth whitening catalytic material based on photothermal integrated Fenton reaction according to claim 1, characterized in that: The inert gas in step S4 is selected from one or more of N2, Ar or He.

6. The method for preparing a tooth whitening catalytic material based on photothermal integrated Fenton reaction according to claim 1, characterized in that: The mass ratio of TiO2 to NaBH4 described in step S5 is 4:

3.

7. The method for preparing a tooth whitening catalytic material based on photothermal integrated Fenton reaction according to claim 1, characterized in that: The mixing method in step S6 is one or more of stirring, grinding or sieving.

8. A tooth whitening catalytic material based on photothermal integrated Fenton reaction obtained according to the preparation method of any one of claims 1 to 7.

9. A use of the tooth whitening catalytic material based on the photothermal integrated Fenton reaction as claimed in claim 8 in the preparation of tooth whitening products, characterized in that: By bringing the teeth whitening catalytic material into contact with the teeth and irradiating them with a teeth whitening device containing blue light with a wavelength of 450-480 nm for a period of time, the photocatalytic effect of the material will be stimulated to produce hydroxyl free radicals, which will degrade the organic matter and pigments on the surface of the teeth and achieve a teeth whitening effect.

10. Use of the tooth whitening catalytic material based on the photothermal integrated Fenton reaction according to claim 9 in the preparation of tooth whitening products, characterized in that, The teeth whitening products include toothpaste, tooth strips, gel containing the above materials, as well as medical braces, toothbrushes and teeth whitening devices added with the above materials.

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