Anti-allergic whitening toothpaste and preparation method and application thereof

Abstract

This invention relates to the field of oral care technology, specifically to an anti-sensitivity whitening toothpaste, its preparation method, and its application. The anti-sensitivity whitening toothpaste comprises components such as dual-enzyme modified silica, bacterial fermentation broth, and anti-sensitivity and anti-caries additives. The dual-enzyme modified silica is prepared by amylation and carboxylation modification of hydrated silica, followed by loading with bamboo leaf flavonoids and immobilizing glucose oxidase and catalase. The bacterial fermentation broth is prepared by the combined fermentation of plant extracts by *Roseola mucosa* and *Lactobacillus rhamnosus*. This invention utilizes dual-enzyme catalysis to generate low-concentration reactive oxygen species in situ from salivary glucose to achieve gentle whitening. Bamboo leaf flavonoids and chemically modified carriers synergistically protect enzyme activity. The combined bacterial fermentation broth regulates the oral microecology and, in conjunction with strontium acetate and sodium fluoride, achieves triple anti-sensitivity and anti-caries effects. The components synergistically enhance the effects, providing whitening, anti-sensitivity, and gum-nourishing benefits. Furthermore, the toothpaste exhibits good stability and is suitable for industrial production.

Description

Technical Field

[0001] This invention relates to the field of oral care technology, specifically to an anti-sensitivity whitening toothpaste and its preparation method and application. Background Technology

[0002] Teeth whitening and desensitization are core needs in the modern oral care field, and consumers are increasingly eager for oral care products that combine gentle whitening, long-lasting desensitization, and comprehensive gum care.

[0003] Currently, teeth whitening primarily relies on two approaches: First, chemical bleaching using strong oxidizing agents such as high-concentration hydrogen peroxide. While this method is fast-acting, it can easily lead to enamel demineralization, tooth sensitivity, and even damage to the dental pulp, posing a potential threat to enamel integrity and oral soft tissues, making it unsuitable for long-term use by sensitive individuals. Second, removing extrinsic stains from the tooth surface using physical abrasives. However, large-particle, high-hardness abrasives (such as calcium carbonate) can wear down enamel with prolonged use and are difficult to remove pigments that have penetrated into the enamel. In recent years, bio-enzyme whitening technology has gained widespread attention due to its gentleness; however, free enzymes exhibit low activity and are easily deactivated in the complex environment of toothpaste, limiting their application effectiveness.

[0004] In the fields of anti-allergy and gum care, common anti-allergy ingredients such as potassium salts, while relieving sensitivity, have a relatively slow onset of action. Chemical drugs or single plant extracts used for anti-inflammatory and swelling-reducing purposes have relatively limited functions and are insufficient to comprehensively address complex problems caused by oral microecological imbalances, such as gingival redness and bleeding. Although probiotic technology has been proven to regulate oral flora balance, its effects are often independent of those of plant extracts, lacking a synergistic mechanism and failing to achieve the combined functions of "enzyme protection, anti-inflammation, and gum care."

[0005] Based on the above statements, there is an urgent need to provide an anti-sensitivity whitening toothpaste and its preparation method. Summary of the Invention

[0006] To address the problems of traditional whitening toothpaste being highly irritating and easily causing dentin hypersensitivity and enamel damage, and simple anti-sensitivity toothpaste lacking whitening and gum-nourishing functions, existing enzyme-catalyzed and probiotic products suffer from easy degradation of enzyme activity, poor paste stability, and the disconnect between natural ingredients and probiotics, making it difficult to achieve multiple effects such as whitening, anti-sensitivity, and gum nourishment, this invention provides an anti-sensitivity whitening toothpaste, its preparation method, and its application.

[0007] In a first aspect, the present invention provides an anti-sensitivity whitening toothpaste, which adopts the following technical solution: An anti-sensitivity whitening toothpaste comprises the following raw materials in weight percentages: 15-20% dual-enzyme modified silica, 3-5% bacterial fermentation broth, 1.5-2.5% anti-sensitivity and anti-caries adjuvant, 1.5-2.5% detergent, 20-25% moisturizer, 2-3% stabilizer, 0.5-1% sensory modifier, 0.3-0.5% preservative, with the balance being deionized water.

[0008] Preferably, the method for preparing the dual-enzyme modified silica includes the following steps: A1. Add hydrated silica and γ-aminopropyltriethoxysilane to deionized water, disperse by ultrasonication, adjust pH to 4.0-5.0, reflux reaction, centrifuge, wash precipitate to obtain aminated hydrated silica; A2. Disperse aminated hydrated silica in a buffer solution with a pH of 7.0-7.4, add succinic anhydride, stir the reaction, centrifuge, wash the precipitate, and obtain carboxylated hydrated silica. A3. Disperse carboxylated hydrated silica in a buffer solution with a pH of 8.0-9.0, add bamboo leaf flavonoid extract, stir and react, centrifuge, wash the precipitate, and obtain bamboo leaf flavonoid-loaded hydrated silica. A4. Disperse bamboo leaf flavonoid-loaded hydrated silica in a buffer solution with a pH of 6.0-7.0, add EDC and NHS in sequence, activate at room temperature, then add the dual-enzyme system, stir the reaction at room temperature in the dark, centrifuge, wash the precipitate, and obtain dual-enzyme modified silica.

[0009] Preferably, in step A1, the mass-to-volume ratio of hydrated silica, γ-aminopropyltriethoxysilane, and deionized water is 100g:3-5g:200-300mL.

[0010] Preferably, the reflux reaction temperature in step A1 is 70-80℃, and the reflux reaction time is 4-6h.

[0011] Preferably, in step A2, the mass-to-volume ratio of aminated hydrated silica, buffer solution, and succinic anhydride is 100g: 2000-3000mL: 5-8g.

[0012] Preferably, in step A2, the stirring speed is 200-400 rpm and the stirring time is 2-3 hours.

[0013] Preferably, in step A3, the mass-to-volume ratio of carboxylated hydrated silica, buffer solution, and bamboo leaf flavonoid extract is 100g: 2000-3000mL: 3-6g.

[0014] Preferably, in step A3, the stirring reaction temperature is 30-35℃, the stirring reaction speed is 200-400 rpm, and the stirring reaction time is 3-4 hours.

[0015] Preferably, in step A4, bamboo leaf flavonoids are loaded with hydrated silica, buffer solution, EDC, and NHS. The mass-to-volume ratio of the two-enzyme system is 100g: 2000-3000mL: 4-7g: 5-8g: 3-5g.

[0016] Preferably, the dual-enzyme system in step A4 consists of glucose oxidase with an enzyme activity ≥100U / mg and catalase with an enzyme activity ≥200U / mg in a mass ratio of 3-4:1-2.

[0017] Preferably, the method for preparing the microbial fermentation broth includes the following steps: Plant extracts were added to deionized water, ultrasonically dispersed, and filtered to remove bacteria to obtain a plant extract suspension. The plant extract suspension and the bacterial culture solution were added to MRS liquid culture medium, anaerobically cultured, centrifuged, and the supernatant was collected and filtered to obtain the bacterial fermentation broth.

[0018] Preferably, the preparation of the microbial fermentation broth specifically includes the following steps: Plant extracts were added to deionized water to prepare a plant extract suspension with a mass concentration of 5-8 mg / mL. The suspension was ultrasonically dispersed at 300-400 W for 15-20 min and then filtered through a 0.22-0.45 μm filter membrane for sterilization to obtain the plant extract suspension. The plant extract suspension and the bacterial culture were added to MRS liquid culture medium at a volume ratio of 5-8:2-3:100. After anaerobic culture at 37-38℃ for 24-30 h, the mixture was centrifuged at 8000-10000 rpm for 15-20 min. The supernatant was collected and filtered through a 0.22-0.45 μm filter membrane to obtain the bacterial fermentation broth.

[0019] Preferably, the plant extract is selected from one or more of the following: Lophatherum gracile extract, Paris polyphylla extract, Panax notoginseng extract, Lonicera japonica extract, Scutellaria baicalensis extract, and Phellodendron amurense extract.

[0020] Preferably, the plant extract is composed of Lophatherum gracile extract, Paris polyphylla extract and Panax notoginseng extract in a mass ratio of 1-2:1-3:1-2.

[0021] Preferably, the bacterial composite seed liquid contains ≥1×10⁻⁶ viable bacteria. 8 CFU / mL of *Rhodesia mucosa* bacterial suspension and viable count ≥1×10⁻⁶ 8 The bacterial culture of Lactobacillus rhamnosus with a concentration of CFU / mL was composed of a volume ratio of 1:1-1.4.

[0022] Preferably, the anti-allergy and anti-caries adjuvant is composed of strontium acetate, sodium fluoride and paeonol-β-cyclodextrin inclusion complex in a mass ratio of 3-5:1:1-2.

[0023] Preferably, the preparation method of the paeonol-β-cyclodextrin inclusion complex is as follows: Add β-cyclodextrin to deionized water, heat to 60-65℃, stir at 200-400 rpm until dissolved, cool to room temperature, and prepare a saturated β-cyclodextrin solution. Disperse paeonol in anhydrous ethanol at a mass-to-volume ratio of 1 g: 5-10 mL to obtain a paeonol solution. Add the paeonol solution dropwise to the β-cyclodextrin solution under light-protected conditions and stirring at 200-400 rpm for 2-4 hours, with the molar ratio of paeonol to β-cyclodextrin being 1:8-12. Continue stirring under light-protected conditions for 2-4 hours, then refrigerate at 4-8℃ for 12-24 hours, filter, wash the precipitate 1-2 times with anhydrous ethanol, and vacuum dry at 0.06-0.08 MPa and 40-50℃ for 4-6 hours to obtain the paeonol-β-cyclodextrin inclusion complex.

[0024] Preferably, the cleaning agent is selected from one or more of sodium lauryl sulfate, cocamidopropyl betaine, and disodium cocoyl glutamate.

[0025] Preferably, the moisturizer is composed of sorbitol, glycerin and polyethylene glycol-8 in a mass ratio of 14-18:3-5:4-5.

[0026] Preferably, the stabilizer is composed of cellulose gum, poloxamer, and trisodium phosphate in a mass ratio of 5-7:2-3:1.

[0027] Preferably, the sensory modifier is composed of flavoring, CI 77891 and trichlorogalactose in a mass ratio of 1-3:2-5:2-4.

[0028] Preferably, the preservative is composed of sodium ethylparaben, sodium propylparaben, and 1,2-hexanediol in a mass ratio of 1-3:1-2:4-6.

[0029] Secondly, the present invention provides a method for preparing the anti-sensitivity and whitening toothpaste as described above, using the following technical solution: A method for preparing an anti-sensitivity whitening toothpaste includes the following steps: S1. Mix preservatives, humectants, stabilizers with deionized water, heat and stir to dissolve, then cool to form a basic colloid; S2. Add the dual-enzyme modified silica, bacterial fermentation broth, anti-allergy and anti-caries adjuvant, and cleaning agent to the base colloid, stir evenly, then add the sensory modifier, adjust the pH to 6.5-7.0, stir evenly, and obtain the mixture. S3. After vacuum degassing the mixture, fill it into the container to obtain the anti-sensitivity whitening toothpaste.

[0030] Preferably, in step S1, the temperature is raised to 60-65℃, the stirring speed is 300-400 rpm, the stirring time is 30-45 min, and the temperature is cooled to 25-30℃.

[0031] Preferably, in step S2, the stirring speed is 500-600 rpm and the stirring time is 30-40 min.

[0032] Preferably, in step S3, the vacuum degree of vacuum degassing is -0.09 MPa to -0.08 MPa, the degassing temperature is 25-30°C, and the degassing time is 25-35 min. Thirdly, the present invention provides an application of the anti-sensitivity and whitening toothpaste described above in the preparation of oral care products.

[0033] In summary, compared with the prior art, the present invention has the following beneficial effects: (1) Achieving gentle and long-lasting whitening while avoiding enamel damage. This invention uses dual-enzyme modified silica as the core whitening ingredient. Through a specific process, hydrated silica is modified by amination and carboxylation, and loaded with bamboo leaf flavonoids, glucose oxidase, and catalase to construct a stable dual-enzyme catalytic system. This system can utilize the natural glucose in oral saliva to continuously generate low concentrations of reactive oxygen species (ROS), gently oxidizing and decomposing pigment deposits on the tooth surface without the need to add high concentrations of chemical oxidants, thus reducing the corrosion of enamel and the stimulation of dentin from the root. At the same time, the synergistic effect of bamboo leaf flavonoids and the modified carrier can effectively protect the activity of the dual enzymes, prolong the whitening effect, and solve the pain points of easy degradation of enzyme activity and short whitening effect in existing enzyme-catalyzed whitening products, thus achieving long-lasting and gentle whitening.

[0034] (2) Constructing a triple anti-sensitivity and anti-caries system with significant and lasting anti-sensitivity and anti-caries effects. This invention uses strontium acetate, sodium fluoride, and paeonol-β-cyclodextrin inclusion complex in a specific ratio to form an anti-sensitivity and anti-caries adjuvant. Strontium acetate can block the conduction of dentin nerves and quickly relieve dentin sensitivity; sodium fluoride can promote enamel mineralization, enhance the acid resistance of teeth, and effectively prevent tooth decay; paeonol-β-cyclodextrin inclusion complex can avoid the pungent irritation and volatility of free paeonol, and gently exert anti-inflammatory and analgesic effects to help relieve gingival irritation. The three work together to form a triple protection of "analgesia-mineralization-anti-inflammation". Compared with a single anti-sensitivity component, the anti-sensitivity and anti-caries effect is more comprehensive and lasting, which is suitable for the core needs of people with sensitive mouths.

[0035] (3) Achieving synergistic gingival nourishment and long-term regulation of oral microecology through natural ingredients and probiotics. The fermented liquid prepared by this invention uses a compound probiotic of *Rhododendron mucosae* and *Lactobacillus rhamnosus* in coupled fermentation with plant extracts such as *Lophatherum gracile* and *Paris polyphylla*, which solves the problem of the separation between the effects of natural plant ingredients and probiotics in traditional formulas. Flavonoids and steroidal saponins in plant extracts can provide nutritional substrates for compound probiotics, promote their secretion of nitrite reductase, extracellular polysaccharides and antibacterial metabolites, and at the same time, can synergistically stabilize the spatial structure of the two enzymes in the formula and reduce enzyme activity loss; the fermentation of compound probiotics can also degrade the plant macromolecular active substances into easily absorbed aglycones and small molecule products, enhance the anti-inflammatory, antibacterial and gingival repair effects, bidirectionally regulate the balance of oral flora, improve discomfort such as gingival redness and bleeding, and ultimately achieve integrated synergistic optimization of whitening, anti-sensitivity and gingival nourishment effects.

[0036] (4) Constructing an enzyme-microbe bidirectional synergistic system to achieve deep integration of whitening, anti-allergy, and gingival nourishment functions. This invention overcomes the limitations of existing technologies that separate enzyme-catalyzed whitening and microbial gingival nourishment functions through the organic combination of dual-enzyme modified silica and microbial fermentation broth. Specific metabolites in the microbial fermentation broth (such as nitrite reductase, extracellular polysaccharides, antibacterial metabolites, etc.) can form an "antioxidant-protective enzyme microenvironment" with bamboo leaf flavonoids on the surface of dual-enzyme modified silica, enhancing the tolerance and durability of the dual enzymes in the oral environment; at the same time, the trace amount of hydrogen peroxide produced by dual-enzyme catalysis can activate the catalase system of *Roseidon mucosae*, promoting the oxidative transformation and absorption of active ingredients in the microbial fermentation broth, and improving its bioavailability. The two form a positive cycle system of "enzyme-catalyzed metabolite transformation - metabolite-protective enzyme activity", achieving synergistic enhancement and deep integration of the three major functions of whitening, anti-allergy, and gingival nourishment.

[0037] (5) The formula has strong stability, is suitable for industrial production, and provides a good user experience. This invention uses cellulose gum, poloxamer, and trisodium phosphate in a specific ratio to form a stabilizer, combined with an optimized ratio of humectants and preservatives, which can effectively improve the stability of the paste and avoid phenomena such as layering, oiling, and watering, ensuring that active ingredients such as dual enzymes and bacterial fermentation broth maintain their activity during storage and use; at the same time, the ratio of detergents and sensory modifiers is optimized to reduce product irritation and improve the foaming, smoothness, and taste of the paste, making it suitable for use by various oral health groups; all raw materials are conventional raw materials in the oral care field, the preparation process is simple, no special equipment is required, the production cost is low, and it is suitable for large-scale industrial mass production. Detailed Implementation

[0038] The present invention will be further described in detail below with reference to embodiments. It should be understood that the specific embodiments described herein are for illustrative purposes only and are not intended to limit the scope of the invention.

[0039] Where specific techniques or conditions are not specified in the examples, they shall be performed in accordance with the techniques or conditions described in the literature in this field, or in accordance with the product instructions. Reagents or instruments whose manufacturers are not specified are all conventional products that can be purchased through legitimate channels.

[0040] Unless otherwise specified, the experimental methods used in the following embodiments are conventional methods. Unless otherwise specified, the experimental materials used in the following embodiments are commercially available products.

[0041] Among them, Rothia mucilaginosa, ATCC 25296, was purchased from Wuhan Gray Algae Biotechnology Co., Ltd. Lactobacillus rhamnosus, ATCC 53103, was purchased from Wuhan Gray Algae Biotechnology Co., Ltd. Glucose oxidase was purchased from Shanghai Yuanye Biotechnology, product number: S10020; Catalase was purchased from Aladdin, product number: C163049; Hydrated silica was purchased from Guangzhou Aikepu New Materials Co., Ltd., model: TP38; Bamboo leaf flavonoid extract was purchased from Zhejiang Shengshi Biotechnology Co., Ltd. The extract of Lophatherum gracile was purchased from Shaanxi Huachen Biotechnology Co., Ltd. The extract of Paris polyphylla from Yunnan was purchased from Shaanxi Pinhong Biotechnology Co., Ltd. The Panax notoginseng extract was purchased from Shaanxi Xintianyu Biotechnology Co., Ltd. Polyethylene glycol-8 was purchased from Hubei Zhenbo Chemical Co., Ltd. CI 77891 was purchased from Shandong Yousuo Chemical Technology Co., Ltd. The fragrance was purchased from Shanghai Wanxiang Daily Chemical Co., Ltd.

[0042] Example 1 An anti-sensitivity whitening toothpaste comprises the following raw materials in weight percentages: 15% dual-enzyme modified silica, 3% bacterial fermentation broth, 1.5% anti-sensitivity and anti-caries aid, 1.5% detergent, 20% moisturizer, 2% stabilizer, 0.5% sensory modifier, 0.3% preservative, and the balance being deionized water.

[0043] The preparation method of dual-enzyme modified silica includes the following steps: A1. Add hydrated silica and γ-aminopropyltriethoxysilane to deionized water at a mass-to-volume ratio of 100g:3g:200mL, sonicate at 300W for 20min, adjust the pH to 4.0 with 0.2mol / L hydrochloric acid, reflux at 70℃ for 4h, centrifuge at 8000rpm for 10min, wash the precipitate twice with deionized water to obtain aminated hydrated silica; A2. Disperse the amino-hydrated silica in 0.1 mol / L PBS buffer at pH 7.0 according to the mass-volume ratio of 100 g: 2000 mL: 5 g, then add succinic anhydride, stir at 200 rpm for 2 h at room temperature, centrifuge at 8000 rpm for 10 min, wash the precipitate twice with deionized water to obtain carboxylated hydrated silica. A3. Disperse carboxylated hydrated silica in PBS buffer at pH 8.0 according to the mass-volume ratio of 100g:2000mL:3g, add bamboo leaf flavonoid extract, stir at 30℃ and 200rpm for 3h, centrifuge at 8000rpm for 10min, wash the precipitate twice with deionized water to obtain bamboo leaf flavonoid-loaded hydrated silica. A4. The mass-to-volume ratio of bamboo leaf flavonoid-loaded hydrated silica, PBS buffer, EDC, NHS, and the dual-enzyme system was 100g:2000mL:4g:5g:3g. The bamboo leaf flavonoid-loaded hydrated silica was dispersed in PBS buffer at pH 6.0. EDC and NHS were added sequentially, and the mixture was activated at room temperature for 1 hour. Then, the dual-enzyme system (composed of glucose oxidase with an enzyme activity of 100U / mg and catalase with an enzyme activity of 200U / mg in a mass ratio of 3:1) was added. The mixture was stirred at 200 rpm at room temperature in the dark for 2 hours. After stirring, the mixture was centrifuged at 8000 rpm for 10 minutes. The precipitate was washed twice with deionized water to obtain the dual-enzyme modified silica.

[0044] The preparation of the microbial fermentation broth specifically includes the following steps: Plant extracts (composed of Lophatherum gracile extract, Paris polyphylla extract, and Panax notoginseng extract in a mass ratio of 1:1:1) were added to deionized water to prepare a plant extract suspension with a mass concentration of 5 mg / mL. The suspension was ultrasonically dispersed at 300 W for 15 min and then filtered through a 0.22 μm filter membrane for sterilization to obtain the plant extract suspension. The plant extract suspension and a bacterial culture (composed of 1 × 10⁻⁶ viable bacteria) were then added at a volume ratio of 5:2:100. 8 The CFU / mL concentration of *Rhodesia mucinosa* bacterial suspension and the viable count were 1×10⁻⁶. 8 A 1:1 ratio of CFU / mL Lactobacillus rhamnosus culture was added to MRS liquid medium and anaerobic cultured at 37°C for 24 h. After centrifugation at 8000 rpm for 15 min, the supernatant was collected and filtered through a 0.22 μm filter membrane to obtain the bacterial fermentation broth.

[0045] The anti-allergy and anti-caries adjuvant is composed of strontium acetate, sodium fluoride, and paeonol-β-cyclodextrin inclusion complex in a mass ratio of 3:1:1. The preparation method of paeonol-β-cyclodextrin inclusion complex is as follows: β-cyclodextrin is added to deionized water, heated to 60℃, stirred at 200 rpm until dissolved, and cooled to room temperature to prepare a saturated β-cyclodextrin solution; paeonol is ultrasonically dispersed in anhydrous ethanol at a mass-volume ratio of 1 g: 5 mL to obtain a paeonol solution; under light-protected conditions and stirring at 200 rpm, the paeonol solution is added dropwise to the β-cyclodextrin solution, and the addition time is controlled to be 2 h, wherein the molar ratio of paeonol to β-cyclodextrin is 1:8; after stirring in the dark for another 2 h, it is refrigerated at 4℃ and allowed to stand for 12 h, filtered, the precipitate is washed once with anhydrous ethanol, and dried under vacuum at 0.06 MPa and 40℃ for 4 h to obtain the paeonol-β-cyclodextrin inclusion complex.

[0046] The cleaning agent is sodium lauryl sulfate.

[0047] The moisturizer consists of sorbitol, glycerin and polyethylene glycol-8 in a mass ratio of 14:3:4.

[0048] The stabilizer consists of cellulose gum, poloxamer, and trisodium phosphate in a mass ratio of 5:2:1.

[0049] The sensory modifier consists of flavoring, CI 77891 and trichlorogalactose in a mass ratio of 1:2:2.

[0050] The preservative consists of sodium ethylparaben, sodium propylparaben, and 1,2-hexanediol in a mass ratio of 1:1:4.

[0051] A method for preparing an anti-sensitivity whitening toothpaste includes the following steps: S1. Mix the preservative, humectant, stabilizer and deionized water, heat to 60°C, stir at 300 rpm for 30 min, and then cool to 25°C to form a basic colloid. S2. Add the dual-enzyme modified silica, bacterial fermentation broth, anti-allergy and anti-caries adjuvant and cleaning agent to the basic colloid, stir at 500 rpm for 30 min, then add sensory modifier, adjust the pH to 6.5 with 5 wt% trisodium phosphate aqueous solution, stir at 500 rpm for 30 min to obtain the mixture; S3. After degassing the mixture under vacuum at -0.09MPa and 25℃ for 25 minutes, fill the package to obtain the anti-sensitivity whitening toothpaste.

[0052] Example 2 An anti-sensitivity whitening toothpaste comprises the following raw materials in weight percentages: 18% dual-enzyme modified silica, 4% bacterial fermentation broth, 2% anti-sensitivity and anti-caries aid, 2% detergent, 22% moisturizer, 2.5% stabilizer, 0.75% sensory modifier, 0.4% preservative, and the balance being deionized water.

[0053] The preparation method of dual-enzyme modified silica includes the following steps: A1. Add hydrated silica and γ-aminopropyltriethoxysilane to deionized water at a mass-to-volume ratio of 100g:4g:250mL, sonicate at 350W for 25min, adjust the pH to 4.5 with 0.3mol / L hydrochloric acid, reflux at 75℃ for 5h, centrifuge at 9000rpm for 12min, wash the precipitate three times with deionized water to obtain aminated hydrated silica; A2. Disperse aminated hydrated silica in 0.1 mol / L PBS buffer at pH 7.2 according to the mass-volume ratio of 100 g: 2500 mL: 6 g, then add succinic anhydride, stir at 300 rpm for 2.5 h at room temperature, centrifuge at 9000 rpm for 12 min, and wash the precipitate three times with deionized water to obtain carboxylated hydrated silica. A3. Disperse carboxylated hydrated silica in PBS buffer at pH 8.5 according to a mass-volume ratio of 100g:2500mL:5g, add bamboo leaf flavonoid extract, stir at 32℃ and 300rpm for 3.5h, centrifuge at 9000rpm for 12min, wash the precipitate three times with deionized water to obtain bamboo leaf flavonoid-loaded hydrated silica. A4. The mass-to-volume ratio of bamboo leaf flavonoid-loaded hydrated silica, PBS buffer, EDC, NHS, and the dual-enzyme system was 100g:2500mL:5g:6g:4g. The bamboo leaf flavonoid-loaded hydrated silica was dispersed in PBS buffer at pH 6.5. EDC and NHS were added sequentially, and the mixture was activated at room temperature for 1.5h. Then, the dual-enzyme system (composed of glucose oxidase with an enzyme activity of 100U / mg and catalase with an enzyme activity of 200U / mg in a mass ratio of 3.5:1.5) was added. The mixture was stirred at 250rpm at room temperature in the dark for 2.5h. After centrifugation at 9000rpm for 12min, the precipitate was washed three times with deionized water to obtain the dual-enzyme modified silica.

[0054] The preparation of the microbial fermentation broth specifically includes the following steps: Plant extracts (composed of Lophatherum gracile extract, Paris polyphylla extract, and Panax notoginseng extract in a mass ratio of 1.5:2:1.5) were added to deionized water to prepare a plant extract suspension with a mass concentration of 6 mg / mL. The suspension was ultrasonically dispersed at 350 W for 18 min and then filtered through a 0.22 μm filter membrane for sterilization to obtain the plant extract suspension. The plant extract suspension and a bacterial culture (composed of 1 × 10⁻⁶ viable bacteria) were then added at a volume ratio of 6:2.5:100. 8 The CFU / mL concentration of *Rhodesia mucinosa* bacterial suspension and the viable count were 1×10⁻⁶. 8A CFU / mL Lactobacillus rhamnosus culture solution (composed at a volume ratio of 1:1.2) was added to MRS liquid medium. After anaerobic culture at 37°C for 28 h, the culture was centrifuged at 9000 rpm for 18 min. The supernatant was collected and filtered through a 0.22 μm filter membrane to obtain the bacterial fermentation broth.

[0055] The anti-allergy and anti-caries adjuvant is composed of strontium acetate, sodium fluoride, and paeonol-β-cyclodextrin inclusion complex in a mass ratio of 4:1:1.5. The preparation method of paeonol-β-cyclodextrin inclusion complex is as follows: β-cyclodextrin is added to deionized water, heated to 62℃, stirred at 300 rpm until dissolved, and cooled to room temperature to prepare a saturated β-cyclodextrin solution; paeonol is ultrasonically dispersed in anhydrous ethanol at a mass-volume ratio of 1 g:8 mL to obtain a paeonol solution; under light-protected conditions and stirring at 300 rpm, the paeonol solution is added dropwise to the β-cyclodextrin solution, and the addition time is controlled to be 3 h, wherein the molar ratio of paeonol to β-cyclodextrin is 1:10; after stirring in the dark for another 3 h, the mixture is refrigerated at 6℃ for 18 h, filtered, the precipitate is washed twice with anhydrous ethanol, and dried under vacuum at 0.07 MPa and 45℃ for 5 h to obtain the paeonol-β-cyclodextrin inclusion complex.

[0056] The cleaning agent is sodium lauryl sulfate.

[0057] The moisturizer consists of sorbitol, glycerin and polyethylene glycol-8 in a mass ratio of 16:4:4.5.

[0058] The stabilizer consists of cellulose gum, poloxamer, and trisodium phosphate in a mass ratio of 6:2.5:1.

[0059] The sensory modifier consists of flavoring, CI 77891 and trichlorogalactose in a mass ratio of 2:4:3.

[0060] The preservative consists of sodium ethylparaben, sodium propylparaben, and 1,2-hexanediol in a mass ratio of 2:1.5:5.

[0061] A method for preparing an anti-sensitivity whitening toothpaste includes the following steps: S1. Mix the preservative, humectant, stabilizer and deionized water, heat to 62°C, stir at 350 rpm for 40 min, and then cool to 28°C to form a basic colloid. S2. Add the dual-enzyme modified silica, bacterial fermentation broth, anti-allergy and anti-caries adjuvant and cleaning agent to the basic colloid, stir at 550 rpm for 35 min, then add the sensory modifier, adjust the pH to 6.8 with 7.5 wt% trisodium phosphate aqueous solution, stir at 550 rpm for 35 min to obtain the mixture; S3. After degassing the mixture under vacuum at -0.08MPa and 28℃ for 30 minutes, fill the package to obtain the anti-sensitivity whitening toothpaste.

[0062] Example 3 An anti-sensitivity whitening toothpaste comprises the following raw materials in weight percentages: 20% dual-enzyme modified silica, 5% bacterial fermentation broth, 2.5% anti-sensitivity and anti-caries aid, 2.5% detergent, 25% moisturizer, 3% stabilizer, 1% sensory modifier, 0.5% preservative, and the balance being deionized water.

[0063] The preparation method of dual-enzyme modified silica includes the following steps: A1. Add hydrated silica and γ-aminopropyltriethoxysilane to deionized water at a mass-to-volume ratio of 100g:5g:300mL, sonicate at 400W for 30min, adjust the pH to 5.0 with 0.4mol / L hydrochloric acid, reflux at 80℃ for 6h, centrifuge at 10000rpm for 15min, wash the precipitate 4 times with deionized water to obtain aminated hydrated silica; A2. Disperse aminated hydrated silica in 0.1 mol / L PBS buffer at pH 7.4 according to the mass-volume ratio of 100 g: 3000 mL: 8 g, then add succinic anhydride, stir at 400 rpm for 3 h at room temperature, centrifuge at 10000 rpm for 15 min, and wash the precipitate 4 times with deionized water to obtain carboxylated hydrated silica. A3. Disperse carboxylated hydrated silica in PBS buffer at pH 9.0 according to the mass-volume ratio of 100g:3000mL:6g, add bamboo leaf flavonoid extract, stir at 35℃ and 400rpm for 4h, centrifuge at 10000rpm for 15min, wash the precipitate 4 times with deionized water to obtain bamboo leaf flavonoid-loaded hydrated silica. A4. The mass-to-volume ratio of bamboo leaf flavonoid-loaded hydrated silica, PBS buffer, EDC, NHS, and the dual-enzyme system was 100g:3000mL:7g:8g:5g. The bamboo leaf flavonoid-loaded hydrated silica was dispersed in PBS buffer at pH 7.0. EDC and NHS were added sequentially, and the mixture was activated at room temperature for 2 hours. Then, the dual-enzyme system (composed of glucose oxidase with an enzyme activity of 100U / mg and catalase with an enzyme activity of 200U / mg in a mass ratio of 4:2) was added. The mixture was stirred at 300 rpm at room temperature in the dark for 3 hours. After centrifugation at 10000 rpm for 15 minutes, the precipitate was washed 4 times with deionized water to obtain the dual-enzyme modified silica.

[0064] The preparation of the microbial fermentation broth specifically includes the following steps: Plant extracts (composed of Lophatherum gracile extract, Paris polyphylla extract, and Panax notoginseng extract in a mass ratio of 2:3:2) were added to deionized water to prepare a plant extract suspension with a mass concentration of 8 mg / mL. The suspension was ultrasonically dispersed at 400 W for 20 min and then filtered through a 0.45 μm filter membrane for sterilization to obtain the plant extract suspension. The plant extract suspension and a bacterial culture (composed of 1 × 10⁻⁶ viable bacteria) were then added at a volume ratio of 8:3:100. 8 The CFU / mL concentration of *Rhodesia mucinosa* bacterial suspension and the viable count were 1×10⁻⁶. 8 A CFU / mL Lactobacillus rhamnosus culture solution (composed at a volume ratio of 1:1.4) was added to MRS liquid medium. After anaerobic culture at 38℃ for 30 h, the culture was centrifuged at 10000 rpm for 20 min. The supernatant was collected and filtered through a 0.22 μm filter membrane to obtain the bacterial fermentation broth.

[0065] The anti-allergy and anti-caries adjuvant is composed of strontium acetate, sodium fluoride, and paeonol in a mass ratio of 5:1:2. The preparation method of the paeonol-β-cyclodextrin inclusion complex is as follows: β-cyclodextrin is added to deionized water, heated to 65℃, stirred at 400 rpm until dissolved, and cooled to room temperature to prepare a saturated β-cyclodextrin solution; paeonol is ultrasonically dispersed in anhydrous ethanol at a mass-volume ratio of 1 g:10 mL to obtain a paeonol solution; under light-protected conditions and stirring at 400 rpm, the paeonol solution is added dropwise to the β-cyclodextrin solution for 4 hours, with the molar ratio of paeonol to β-cyclodextrin being 1:12; after stirring in the dark for another 4 hours, the mixture is refrigerated at 8℃ for 24 hours, filtered, and the precipitate is washed twice with anhydrous ethanol and dried under vacuum at 0.08 MPa and 50℃ for 6 hours to obtain the paeonol-β-cyclodextrin inclusion complex.

[0066] The cleaning agent is sodium lauryl sulfate.

[0067] The moisturizer consists of sorbitol, glycerin and polyethylene glycol-8 in a mass ratio of 18:5:5.

[0068] The stabilizer consists of cellulose gum, poloxamer, and trisodium phosphate in a mass ratio of 7:3:1.

[0069] The sensory modifier consists of flavoring, CI 77891 and trichlorogalactose in a mass ratio of 3:5:4.

[0070] The preservative consists of sodium ethylparaben, sodium propylparaben, and 1,2-hexanediol in a mass ratio of 3:2:6.

[0071] A method for preparing an anti-sensitivity whitening toothpaste includes the following steps: S1. Mix the preservative, humectant, stabilizer and deionized water, heat to 65°C, stir at 400 rpm for 45 minutes, and then cool to 30°C to form a basic colloid. S2. Add the dual-enzyme modified silica, bacterial fermentation broth, anti-allergy and anti-caries adjuvant and cleaning agent to the basic colloid, stir at 600 rpm for 40 min, then add sensory modifier, adjust the pH to 7.0 with 10 wt% trisodium phosphate aqueous solution, stir at 600 rpm for 40 min to obtain the mixture; S3. After degassing the mixture under vacuum at -0.08MPa and 30℃ for 35 minutes, fill the package to obtain the anti-sensitivity whitening toothpaste.

[0072] Comparative Example 1 The only difference between this comparative example and Example 2 is that the dual-enzyme modified silica in step S2 is replaced with an equal mass of ordinary hydrated silica. The remaining raw material ratios, preparation processes, and all parameters are completely consistent with Example 2.

[0073] Comparative Example 2 The only difference between this comparative example and Example 2 is that the bacterial fermentation broth in step S2 is replaced with an equal mass of plant extract suspension. All other raw material ratios, preparation processes, and parameters are completely consistent with Example 2.

[0074] The preparation of plant extract suspensions specifically includes the following steps: The plant extract (composed of Lophatherum gracile extract, Paris polyphylla extract and Panax notoginseng extract in a mass ratio of 1.5:2:1.5) was added to deionized water to prepare a plant extract suspension with a mass concentration of 6 mg / mL.

[0075] Comparative Example 3 The only difference between this comparative example and Example 2 is that step A3 is omitted in the preparation of the dual-enzyme modified silica. The carboxylated hydrated silica obtained in step A2 is directly immobilized with dual enzymes in step A4. The remaining raw material ratios, preparation processes and all parameters are completely consistent with those in Example 2.

[0076] The preparation method of dual-enzyme modified silica includes the following steps: A1. Add hydrated silica and γ-aminopropyltriethoxysilane to deionized water at a mass-to-volume ratio of 100g:4g:250mL, sonicate at 350W for 25min, adjust the pH to 4.5 with 0.3mol / L hydrochloric acid, reflux at 75℃ for 5h, centrifuge at 9000rpm for 12min, wash the precipitate three times with deionized water to obtain aminated hydrated silica; A2. Disperse aminated hydrated silica in 0.1 mol / L PBS buffer at pH 7.2 according to the mass-volume ratio of 100 g: 2500 mL: 6 g, then add succinic anhydride, stir at 300 rpm for 2.5 h at room temperature, centrifuge at 9000 rpm for 12 min, and wash the precipitate three times with deionized water to obtain carboxylated hydrated silica. A3. The carboxylated hydrated silica, PBS buffer, EDC, NHS, and the dual-enzyme system were in a mass-to-volume ratio of 100g:2500mL:5g:6g:4g. The carboxylated hydrated silica was dispersed in PBS buffer at pH 6.5. EDC and NHS were added sequentially, and the mixture was activated at room temperature for 1.5h. Then, the dual-enzyme system (composed of glucose oxidase with an enzyme activity of 100U / mg and catalase with an enzyme activity of 200U / mg in a mass ratio of 3.5:1.5) was added. The mixture was stirred at 250rpm at room temperature in the dark for 2.5h. After centrifugation at 9000rpm for 12min, the precipitate was washed three times with deionized water to obtain the dual-enzyme modified silica.

[0077] Comparative Example 4 The only difference between this comparative example and Example 2 is that, in the preparation process of the dual-enzyme modified silica, the bamboo leaf flavonoid extract in step A3 is replaced with an equal mass of tea polyphenols. The remaining raw material ratios, preparation processes, and all parameters are completely consistent with Example 2.

[0078] Comparative Example 5 The only difference between this comparative example and Example 2 is that the dual-enzyme modified silica in step S2 is replaced with an equal mass of bamboo leaf flavonoid-loaded hydrated silica. The remaining raw material ratios, preparation processes, and all parameters are completely consistent with Example 2.

[0079] The preparation method of bamboo leaf flavonoid-supported hydrated silica includes the following steps: A1. Add hydrated silica and γ-aminopropyltriethoxysilane to deionized water at a mass-to-volume ratio of 100g:4g:250mL, sonicate at 350W for 25min, adjust the pH to 4.5 with 0.3mol / L hydrochloric acid, reflux at 75℃ for 5h, centrifuge at 9000rpm for 12min, wash the precipitate three times with deionized water to obtain aminated hydrated silica; A2. Disperse aminated hydrated silica in 0.1 mol / L PBS buffer at pH 7.2 according to the mass-volume ratio of 100 g: 2500 mL: 6 g, then add succinic anhydride, stir at 300 rpm for 2.5 h at room temperature, centrifuge at 9000 rpm for 12 min, and wash the precipitate three times with deionized water to obtain carboxylated hydrated silica. A3. Disperse carboxylated hydrated silica in PBS buffer at pH 8.5 according to a mass-volume ratio of 100g:2500mL:5g, add bamboo leaf flavonoid extract, stir at 32℃ and 300rpm for 3.5h, centrifuge at 9000rpm for 12min, wash the precipitate three times with deionized water to obtain bamboo leaf flavonoid-loaded hydrated silica.

[0080] Comparative Example 6 The only difference between this comparative example and Example 2 is that the dual-enzyme modified silica in step S2 is replaced with an equal mass mixture, which is composed of carboxylated hydrated silica, bamboo leaf flavonoid extract and dual-enzyme system, and has the same mass as the carboxylated hydrated silica, bamboo leaf flavonoid extract and dual-enzyme system in Example 2. The remaining raw material ratios, preparation processes and all parameters are completely consistent with Example 2.

[0081] Comparative Example 7 The only difference between this comparative example and Example 2 is that the bacterial composite seed liquid used in the preparation of the bacterial fermentation broth is replaced with an equal amount of live bacteria with a count of 1×10⁻⁶. 8 The CFU / mL *Roseobacterium mucinum* culture was prepared, and the remaining raw material ratios, preparation process, and all parameters were completely consistent with those in Example 2.

[0082] Comparative Example 8 The only difference between this comparative example and Example 2 is that the bacterial composite seed liquid used in the preparation of the bacterial fermentation broth is replaced with an equal amount of live bacteria with a count of 1×10⁻⁶. 8 The cFU / mL Lactobacillus rhamnosus culture, and the other raw material ratios, preparation process and all parameters are completely consistent with those in Example 2.

[0083] Performance testing 1. Antibacterial and deodorizing performance test The antibacterial and deodorizing properties of the anti-sensitivity whitening toothpastes prepared in Examples 1-3 and Comparative Examples 1-8 were tested. Antibacterial rate: Antibacterial performance was tested according to the industry standard WS / T 650-2019 "Evaluation Method for Antibacterial and Antimicrobial Effects". The test strains were Staphylococcus aureus (ATCC 6538), Escherichia coli (ATCC 8739) and Candida albicans (ATCC 10231). The quantitative antibacterial test was performed by carrier immersion. Deodorization rate: 66 subjects aged 18-65 years were randomly divided into 11 groups. The subjects were of any gender, with good dental and gingival health, no oral mucosal diseases, no systemic diseases such as digestive system diseases, no periodontal treatment in the past 3 weeks, no habit of drinking alcohol or smoking, and women were not menstruating and had a breath odor value of 130 or above. Determination of baseline breath value T1: Subjects were tested in the morning on an empty stomach without brushing their teeth. Breath values ​​were measured using a hydrogen sulfide analyzer. The measurements were taken three times and the average value was recorded as T1. Determination of breath quality T2 after use: Subjects brushed their teeth using toothpaste prepared in Examples 1-3 and Comparative Examples 1-8, respectively. The amount of toothpaste used was 1.5g, and brushing was completed within 3 minutes. Breath quality was measured immediately after brushing, and the average value was recorded as T2. Deodorization rate calculation formula: T = (T1 - T2) / T1 × 100%; The specific test results are shown in Table 1.

[0084] Table 1. Test results of antibacterial and deodorizing properties of anti-sensitivity whitening toothpaste

[0085] As shown in Table 1, the anti-sensitivity whitening toothpaste prepared in Examples 1-3 of this invention has excellent antibacterial and deodorizing effects. Among them, Example 2 is the best, with an antibacterial rate of over 95% against Staphylococcus aureus, Escherichia coli and Candida albicans, and a deodorizing rate of 86.8%.

[0086] Comparing Example 2 with Comparative Examples 1 and 2, it can be seen that: in Comparative Example 1, ordinary hydrated silica was used instead of dual-enzyme modified silica, resulting in poor antibacterial and deodorizing performance; in Comparative Example 2, unfermented plant extract suspension was used instead of bacterial fermentation broth, resulting in a significant decrease in antibacterial and deodorizing performance. This indicates that dual-enzyme modified silica and bacterial fermentation broth are the core components for achieving excellent performance, and neither can be omitted.

[0087] The comparison between Example 2 and Comparative Examples 3 and 5 shows that the synergistic effect of bamboo leaf flavonoids and the dual-enzyme system is crucial. Comparative Example 3 did not load bamboo leaf flavonoids and Comparative Example 5 did not add the dual-enzyme system, and their antibacterial and deodorizing properties were significantly reduced, proving that a single component cannot achieve the best effect.

[0088] A comparison between Example 2 and Comparative Example 4 shows that Comparative Example 4, which uses tea polyphenols to replace bamboo leaf flavonoids, has lower antibacterial and deodorizing properties than Example 2. This indicates that bamboo leaf flavonoids are irreplaceable and cannot be easily replaced by ordinary polyphenols.

[0089] A comparison between Example 2 and Comparative Example 6 shows that Comparative Example 6, which uses physical mixing instead of chemical modification, exhibits a significant decrease in antibacterial and deodorizing properties, demonstrating the necessity of the chemical modification process in steps A1 to A4. Simple physical mixing cannot achieve the same effect.

[0090] As can be seen from the comparison between Example 2 and Comparative Examples 7 and 8, both Comparative Examples 7 and 8 used single-strain fermentation, and their antibacterial and deodorizing performance was lower than that of Example 2, indicating that the combined use of *Roseobacterium mucinum* and *Lactobacillus rhamnosus* has a synergistic effect.

[0091] 2. Whitening efficacy test The whitening efficacy of the anti-sensitivity whitening toothpastes prepared in Examples 1-3 and Comparative Examples 1-8 was tested. Preparation and grouping of extracted tooth samples: Seventy-seven fresh bovine preincisors with uniform color were selected, ultrasonically cleaned and dried, and then immersed in a staining agent (composed of a 1:1 volume ratio of red wine and coffee) and stained at a constant temperature of 37°C for 7 days. The staining agent was changed daily until a stable dark brown pigmentation formed on the tooth surface (the shade reached Vita shade guide 5M3). The stained teeth were randomly divided into 11 groups of 7 teeth each, corresponding to Examples 1-3 and Comparative Examples 1-8, respectively. Baseline colorimetric determination: The L value of each tooth after staining was measured using a colorimeter. * (Brightness), a * (Red-Green Value), b * (Yellow-blue value), recorded as the initial value; Tooth brushing simulation treatment: An automatic tooth brushing simulator was used, with a load force of 200g, a brushing frequency of 120 times / min, and a brushing stroke of 10mm. Toothpaste for each group was mixed with simulated saliva containing 0.4% glucose at a mass ratio of 1:3 to form a slurry. Tooth samples of the corresponding groups were brushed to simulate brushing in the morning and evening for 14 consecutive days. After each brushing cycle, the samples were soaked in fresh simulated saliva containing 0.4% glucose and stored at 37℃ to simulate the continuous catalytic effect of the two enzymes in the oral cavity during the interoral period. The simulated saliva was replaced once a day. Final colorimetric value determination: After 14 days, the sample was removed, ultrasonically cleaned with deionized water for 5 minutes to remove residual slurry and loose pigments on the surface, and then naturally dried before measuring L again. * (Brightness), a * (Red-Green Value), b * (Yellow-blue value), recorded as the final value; Whitening formula: ;where ΔL * =L * Final value -L * Initial value, Δa * =a * Final value -a * Initial value, Δb * =b * Final value - b * Initial value; the larger the ΔE value, the more significant the whitening effect; at the same time, the number of color level improvement is recorded by referring to the Vita Classical color chart; The specific test results are shown in Table 2.

[0092] Table 2. Test results of the whitening efficacy of anti-sensitivity whitening toothpaste

[0093] As shown in Table 2, the anti-sensitivity whitening toothpastes prepared in Examples 1-3 of this invention have good whitening effects, with Example 2 showing the best whitening effect.

[0094] Comparing Example 2 with Comparative Examples 1 and 2, it is evident that replacing the dual-enzyme modified silica with ordinary hydrated silica, or replacing the bacterial fermentation broth with plant extract suspension, significantly reduces the whitening effect, confirming that the synergy between the two is the core foundation for whitening. Comparing Example 2 with Comparative Examples 3 and 5, it is evident that the lack of bamboo leaf flavonoid-mediated or dual-enzyme system reduces the ΔE value to below 20, demonstrating that the synergistic catalysis of flavonoids and dual enzymes is crucial for pigment decomposition. Comparing Example 2 with Comparative Example 4, it is evident that tea polyphenols cannot replace the specific enzyme-stabilizing and synergistic effect of bamboo leaf flavonoids. Comparing Example 2 with Comparative Example 6, it is evident that physical mixing results in unstable enzyme activity and easy loss, leading to a poorer whitening effect and an associated risk of enamel damage. Comparing Example 2 with Comparative Examples 7 and 8, it is evident that the synergistic effect of single-strain fermentation broth is weaker than that of compound-strain fermentation broth, further verifying the superiority of the fully synergistic system of this invention.

[0095] 3. Enzyme activity stability test The anti-sensitivity whitening toothpastes prepared in Examples 1-3 and Comparative Examples 1-8 were subjected to enzyme activity stability tests: Storage conditions: Take 100g of each anti-sensitivity whitening toothpaste and put it into a sealed sample tube. Set up 3 parallel samples for each group and conduct a static storage test at 25℃ and 60% relative humidity. Avoid light, vibration and damage to the seal during storage. Measurement time points: Samples were taken and tested at 0 months (initial state) and 6 months of storage, respectively; Enzyme activity assay method: Accurately weigh 2.0 g of sample at each time point, add to 50 mL of 0.1 mol / L PBS buffer (pH 6.5), and place in a constant temperature shaker at 25℃ and 150 rpm for 30 min to fully disperse. Then centrifuge at 8000 rpm for 15 min, and take the supernatant as the enzyme activity assay solution. The enzyme activity of glucose oxidase (GOx) was determined by the o-anisidine-peroxidase coupling method. The enzyme activity unit was defined as the amount of enzyme required to catalyze the generation of 1 μmol of hydrogen peroxide per minute at 25℃ and pH 6.5. The enzyme activity of catalase (CAT) was determined by the titanium sulfate method. The enzyme activity unit was defined as the amount of enzyme required to decompose 1 μmol of hydrogen peroxide per minute at 25℃ and pH 6.5. The enzyme activity retention rates of glucose oxidase and catalase were calculated respectively. The formula for calculating enzyme activity retention rate is: Enzyme activity retention rate (%) = (Enzyme activity at 6 months / Initial enzyme activity at 0 months) × 100%; The specific test results are shown in Table 3.

[0096] Table 3. Results of enzyme activity stability test for anti-sensitivity whitening toothpaste

[0097] Note: "-" indicates that the enzyme was not added.

[0098] As shown in Table 3, the anti-sensitivity whitening toothpastes prepared in Examples 1-3 of this invention have excellent enzyme activity stability, with Example 2 showing the best results.

[0099] Comparing Example 2 with Comparative Examples 3 and 4, it is evident that Comparative Example 3, which did not load bamboo leaf flavonoids, and Comparative Example 4, which replaced bamboo leaf flavonoids with tea polyphenols, both showed a significant decrease in the retention rate of the two enzymes. This indicates that bamboo leaf flavonoids have a specific protective effect on the two enzymes and are a key component in maintaining enzyme activity stability. Their protective effect cannot be simply replaced by ordinary polyphenols. Comparing Example 2 with Comparative Example 6, it is evident that Comparative Example 6, which replaced the chemical modification process in steps A1 to A4 with physical mixing, significantly reduced the retention rate of the two enzymes. This proves that chemical modification can achieve stable fixation of the two enzymes, ensuring long-term enzyme activity retention, while simple physical mixing cannot achieve the same stable effect. Comparing Example 2 with Comparative Examples 2, 7, and 8, it is evident that Comparative Example 2 used plant extract suspension instead of bacterial fermentation broth, and Comparative Examples 7 and 8 used a single bacterial strain to prepare bacterial fermentation broth. The retention rates of the two enzymes in all these groups were lower than in Example 2, indicating that the bacterial fermentation broth prepared with a composite bacterial strain can form a synergistic effect with the two-enzyme modified silica, further improving the enzyme activity stability of the system.

[0100] This specific embodiment is merely an explanation of the present invention and is not intended to limit the invention. After reading this specification, those skilled in the art can make modifications to this embodiment without contributing any inventive step, but such modifications are protected by patent law as long as they are within the scope of the claims of the present invention.

Claims

1. An anti-sensitivity whitening toothpaste, characterized in that, The raw materials include the following percentages by weight: 15-20% dual-enzyme modified silica, 3-5% microbial fermentation broth, 1.5-2.5% anti-allergy and anti-caries additives, 1.5-2.5% detergent, 20-25% humectant, 2-3% stabilizer, 0.5-1% sensory modifier, 0.3-0.5% preservative, with the balance being deionized water; The preparation method of the dual-enzyme modified silica includes the following steps: A1. Add hydrated silica and γ-aminopropyltriethoxysilane to deionized water, disperse by ultrasonication, adjust pH to 4.0-5.0, reflux reaction, centrifuge, wash precipitate to obtain aminated hydrated silica; A2. Disperse amino-hydrated silica in buffer solution, add succinic anhydride, stir the reaction, centrifuge, wash the precipitate, and obtain carboxylated hydrated silica. A3. Disperse carboxylated hydrated silica in buffer solution, add bamboo leaf flavonoid extract, stir the reaction, centrifuge, wash the precipitate, and obtain bamboo leaf flavonoid-loaded hydrated silica. A4. Disperse bamboo leaf flavonoid-loaded hydrated silica in buffer solution, add EDC and NHS in sequence, activate, then add the dual enzyme system, stir the reaction in the dark, centrifuge, wash the precipitate, and obtain dual enzyme modified silica. The preparation method of the bacterial fermentation broth includes the following steps: Plant extracts were added to deionized water, ultrasonically dispersed, and filtered to remove bacteria to obtain a plant extract suspension. The plant extract suspension and the bacterial culture solution were added to MRS liquid culture medium, anaerobic cultured, centrifuged, the supernatant was collected, filtered, and the bacterial fermentation broth was obtained. The dual-enzyme system consists of glucose oxidase with an enzyme activity ≥100U / mg and catalase with an enzyme activity ≥200U / mg in a mass ratio of 3-4:1-2. The plant extracts are Lophatherum gracile extract, Paris polyphylla extract, and Panax notoginseng extract; The bacterial species composite seed liquid is composed of 1×10 8 CFU / mL of Roseomonos mucosa bacteria liquid and 1×10 8 CFU / mL of Lactobacillus rhamnosus bacteria liquid in a volume ratio of 1:1-1.

4.

2. The anti-sensitivity whitening toothpaste according to claim 1, characterized in that, The anti-allergy and anti-caries adjuvant is composed of strontium acetate, sodium fluoride, and paeonol-β-cyclodextrin inclusion complex in a mass ratio of 3-5:1:1-2.

3. The anti-sensitive whitening toothpaste according to claim 1, wherein the anti-sensitive whitening toothpaste is a toothpaste for preventing and treating tooth sensitivity and whitening teeth. The stabilizer is composed of cellulose gum, poloxamer, and trisodium phosphate in a mass ratio of 5-7:2-3:

1.

4. A method of preparing the anti-sensitivity whitening toothpaste according to any one of claims 1 to 3, characterized in that, Includes the following steps: S1. Mix preservatives, humectants, stabilizers with deionized water, heat and stir to dissolve, then cool to form a basic colloid; S2. Add the dual-enzyme modified silica, bacterial fermentation broth, anti-allergy and anti-caries adjuvant, and cleaning agent to the base colloid, stir evenly, then add the sensory modifier, adjust the pH to 6.5-7.0, stir evenly, and obtain the mixture. S3. After vacuum degassing the mixture, fill it into the container to obtain the anti-sensitivity whitening toothpaste.

5. The use of an anti-sensitivity whitening toothpaste as described in any one of claims 1-3 in the preparation of oral care products.

Images