PQQ herbal toothpaste for protecting and repairing oral mucosa and process of PQQ herbal toothpaste

Abstract

The invention relates to the technical field of toothpaste, and discloses PQQ herbal toothpaste for protecting and repairing oral mucosa and a process of the PQQ herbal toothpaste for protecting and repairing the oral mucosa. 15 to 25 parts of glycerol; 1-3 parts of lauryl sodium sulfate; 0.5 to 2 parts of carboxymethyl cellulose; 0.1 to 0.5 part of a sweetening agent; 0.5 to 1.5 parts of mint essence; 0.05 to 0.2 part of sodium benzoate; 0.02 to 0.1 part of pyrroloquinoline quinone; the process comprises the following steps: loading PQQ through layered double hydroxide (LDH) and a metal organic framework (MOF), and combining with a chitosan-polyglutamic acid nano-composite and a herbal extracting solution, so that the slow-release stability is optimized; and calcium hydrophosphate, glycerol and a gel matrix are used for enhancing viscosity and cleaning power, so that the PQQ herbal toothpaste is prepared. The viscosity and cleaning power of the toothpaste are improved by combining calcium hydrophosphate and glycerol, slow-release oxidation resistance is realized by adopting PQQ-loaded LDH and a ZIF-8 / beta-cyclodextrin compound, antibacterial and anti-inflammation effects are enhanced by adding plant extracting solutions such as honeysuckle and the like, and the oral care effect and safety are improved.

Description

Technical Field

[0001] The invention relates to the technical field of toothpaste, in particular to a PQQ herbal toothpaste for protecting and repairing oral mucosa and a process thereof. Background Art

[0002] As a daily oral care product, the function of toothpaste has gradually developed from basic cleaning to multifunctional directions such as moisturizing, antibacterial, anti-oxidation and repair. However, there are still some limitations in the existing toothpaste formula. First, in terms of viscosity and lubricity, many toothpastes rely on a single thickener or lubricant, such as carboxymethyl cellulose, xanthan gum, glycerol, etc., but the use of a single component is difficult to take into account both rheology and cleaning effect, which easily leads to the toothpaste texture being too thin or too viscous, thereby affecting the user experience. In addition, although relying solely on traditional lubricating ingredients (such as glycerol) can improve the smoothness of toothpaste to a certain extent, it is difficult to further improve the cleaning ability of toothpaste during use. Therefore, how to optimize the rheology of toothpaste so that it can improve the cleaning effect while having a good sense of use is a problem that needs to be solved in the prior art.

[0003] On the other hand, the stability and sustained release of active ingredients have always been important challenges in oral care products. In traditional oral care products, active ingredients (such as antioxidants, antibacterial agents) are usually added in the form of free molecules or simple dissolutions, but these active ingredients are susceptible to pH changes, enzyme degradation and saliva dilution in the oral environment, resulting in their release too quickly, short action time, and inability to provide lasting repair effects. For example, pyrroloquinoline quinone (PQQ), as a new type of antioxidant and repair factor, has good biological activity, but has low stability in aqueous solution environments and is easily degraded, which greatly reduces its actual efficacy. Therefore, how to delay the release rate of PQQ through a reasonable carrier system and improve its stability, so as to achieve lasting antioxidant and repair effects, is a major technical bottleneck in the current oral care field.

[0004] In addition, the antibacterial components in oral care products have long mainly relied on chemical antibacterial agents (such as chlorhexidine and triclosan). Although they have good antibacterial effects, long-term use may lead to oral flora imbalance, drug resistance problems, and even potential irritation to oral tissues. Therefore, in recent years, natural plant extracts (such as honeysuckle, forsythia, and tangerine peel) have received attention due to their mild antibacterial and anti-inflammatory effects. However, traditional extraction methods often result in unstable effective ingredient content, affecting the final antibacterial efficacy. In addition, the retention time of these plant extracts in the oral cavity is short, making it difficult to form a continuous antibacterial effect. Therefore, how to improve the stability of plant active ingredients, enhance their sustained-release performance, and reduce irritation to oral tissues has become a key problem to be solved in the research and development of oral care products. Therefore, the present invention proposes a PQQ herbal toothpaste for oral mucosa protection and repair and its process to solve the deficiencies of the prior art. Summary of the Invention

[0005] Aiming at the deficiencies of the prior art, the present invention provides a PQQ herbal toothpaste for oral mucosa protection and repair and its process. By the synergistic effect of calcium hydrogen phosphate and glycerol, the rheology of the toothpaste is optimized. The PQQ-loaded layered double hydroxide (LDH) achieves slow release and stability. Natural herbal extracts replace chemical antibacterial agents, effectively improving the use experience, antioxidant repair ability, and safety of oral care of the toothpaste.

[0006] To achieve the above objectives, the present invention is realized through the following technical solutions: A PQQ herbal toothpaste for oral mucosa protection and repair, the toothpaste comprising the following components in parts by mass: calcium hydrogen phosphate: 40 - 50 parts; glycerol: 15 - 25 parts; sodium lauryl sulfate: 1 - 3 parts; carboxymethyl cellulose: 0.5 - 2 parts; sweetener: 0.1 - 0.5 parts; mint essence: 0.5 - 1.5 parts; sodium benzoate: 0.05 - 0.2 parts; pyrroloquinoline quinone: 0.02 - 0.1 parts; honeysuckle extract: 0.02 - 0.1 parts; forsythia extract: 0.02 - 0.1 parts; tangerine peel extract: 0.02 - 0.1 parts; schisandra chinensis extract: 0.02 - 0.1 parts; lophatherum gracile extract: 0.02 - 0.1 parts; isatis root extract: 0.02 - 0.1 parts; licorice extract: 0.02 - 0.1 parts; deionized water: 25 - 35 parts; LDH-loaded PQQ complex: 0.1 - 0.5 parts; ZIF-8: 0.1 - 0.3 parts; β-cyclodextrin: 0.05 - 0.2 parts; chitosan: 0.05 - 0.3 parts; polyglutamic acid: 0.05 - 0.3 parts.

[0007] Calcium hydrogen phosphate:

[0008] Calcium hydrogen phosphate is a common thickening agent and abrasive in toothpaste. It can provide appropriate friction to clean teeth, and at the same time has a good supplementary effect on calcium in the oral cavity. As a mineral, calcium hydrogen phosphate can effectively participate in the repair of tiny damages on the tooth surface. Its particle size is usually controlled within 2 - 10 microns, which can gently remove dirt on the tooth surface during the cleaning process and will not cause excessive damage to tooth enamel.

[0009] The particles of calcium hydrogen phosphate provide an ideal abrasive effect in toothpaste. It helps remove bacteria and dental plaque on the tooth surface through slight friction, and at the same time its mineral components contribute to the repair and strengthening of the tooth surface. Due to the stability of calcium hydrogen phosphate, it can also prevent tooth demineralization and help restore the hardness of tooth enamel.

[0010] Glycerol:

[0011] As a commonly used humectant, glycerol has good hygroscopicity and lubricating effect. It can effectively increase the wetness of toothpaste, improve its use feeling, and prevent the drying of toothpaste, ensuring the smooth and uniform texture of toothpaste.

[0012] The lubricating effect of glycerol not only improves the texture and taste of toothpaste, making it smoother to use, but also helps reduce excessive friction during brushing, avoiding irritation to the gums and oral mucosa. As a moisturizer, glycerol can help maintain the stability and effectiveness of other active ingredients in toothpaste.

[0013] Sodium lauryl sulfate:

[0014] As a surfactant, sodium lauryl sulfate (SLS) can effectively reduce the surface tension of toothpaste, form foam, and increase the cleaning effect during brushing. It can disperse dirt, grease, and bacteria into water, thus effectively removing dirt on the tooth surface.

[0015] SLS enhances its cleaning performance by reducing the surface tension between toothpaste and the oral surface. It can emulsify and dissolve oils, bacteria, and other impurities on the tooth surface, enabling these substances to be carried away with saliva. In addition, the generation of foam can also provide a better mechanical cleaning effect, making the tooth cleaning effect more significant.

[0016] Carboxymethyl cellulose:

[0017] As a thickening agent, carboxymethyl cellulose (CMC) can increase the viscosity of toothpaste, ensuring the applicability and stability of toothpaste. It can not only improve the gelation effect of toothpaste, but also improve the stability of toothpaste and prevent ingredient stratification.

[0018] Carboxymethyl cellulose binds to water molecules through its long-chain molecules to form a highly stable gel system. The thickening effect makes the use of toothpaste smoother and can effectively maintain the distribution of active ingredients. It also ensures that the toothpaste will not quickly drain during use, providing a long-lasting use experience.

[0019] Sweeteners:

[0020] Sweeteners such as xylitol and erythritol are used to adjust the taste of toothpaste to make it more pleasant. These sweeteners can not only provide sweetness but also prevent dry mouth, giving users a better use experience.

[0021] As low-calorie sweeteners, xylitol and erythritol can not only improve the taste but also reduce the formation of dental plaque. These sweeteners are harmless to teeth and will not cause tooth demineralization or increase the risk of dental caries. Xylitol also helps to inhibit the growth of oral bacteria and has a certain antibacterial effect.

[0022] Peppermint essence:

[0023] Peppermint essence not only has a fresh aroma but also brings a cool feeling to the oral cavity during use, making the oral feeling more comfortable after brushing teeth. Peppermint essence can effectively cover up the smell of other ingredients and has a certain refreshing effect on the oral cavity.

[0024] Peppermint essence stimulates the taste and olfactory receptors in the oral cavity to produce a cool feeling, which helps to relieve discomfort in the oral cavity. It also plays a role in local cleaning and keeps the breath fresh. The components of peppermint also have a slight antibacterial effect, which helps to reduce the growth of bacteria in the oral cavity.

[0025] Sodium benzoate:

[0026] As a preservative, sodium benzoate can effectively extend the shelf life of toothpaste and prevent the growth of bacteria and fungi. It can effectively inhibit the growth of microorganisms in toothpaste and maintain the long-term stability of toothpaste.

[0027] Sodium benzoate prevents toothpaste from being contaminated during storage by inhibiting the growth of bacteria and fungi. It interferes with the metabolism of microorganisms to prevent them from multiplying in toothpaste, ensuring the hygienic safety of toothpaste.

[0028] Pyrroloquinoline quinone:

[0029] Pyrroloquinoline quinone (PQQ) is a compound with strong antioxidant activity. It can effectively resist oxidation reactions and plays an important role in the repair and protection of oral mucosa and teeth.

[0030] PQQ, through its powerful antioxidant effect, helps reduce the generation of free radicals in the oral cavity, protecting oral cells from oxidative damage. It helps alleviate gum inflammation, promotes the repair of oral mucosa, and enhances the antibacterial protection function of teeth.

[0031] Extracts of honeysuckle, forsythia, tangerine peel, schisandra chinensis, lophatherum gracile, isatis root, and licorice:

[0032] Extracts of plants such as honeysuckle, forsythia, tangerine peel, schisandra chinensis, lophatherum gracile, isatis root, and licorice contain various active ingredients, which can provide antibacterial, anti-inflammatory, antioxidant, and oral care effects for toothpaste.

[0033] Active ingredients in these plant extracts, such as flavonoids, volatile oils, and polysaccharides, can effectively reduce inflammation in the oral cavity, promote gum health, and provide natural antibacterial effects. They can effectively inhibit the reproduction of bacteria in the oral cavity, reducing problems such as gum bleeding and oral ulcers.

[0034] Deionized water:

[0035] As a solvent, deionized water can effectively dissolve and dilute other components, and provide good fluidity and stability.

[0036] The role of deionized water is to serve as the matrix of toothpaste, helping to disperse and dissolve each component, ensuring that other active ingredients can be evenly distributed. In addition, water also makes the toothpaste have an appropriate viscosity and taste, making it more convenient and comfortable to use.

[0037] LDH loaded with PQQ complex:

[0038] The LDH (layered double hydroxide) loaded with PQQ complex has good biocompatibility and stability, which can enhance the sustained release effect of PQQ in toothpaste.

[0039] As a carrier, LDH can effectively load PQQ and achieve a slow-release effect, enabling the active ingredients of PQQ to be continuously released for a long time, thereby enhancing the antioxidant effect of toothpaste and promoting oral health.

[0040] ZIF-8:

[0041] ZIF-8 is a metal-organic framework (MOF) material with a large specific surface area, which can provide good drug loading and release capabilities.

[0042] ZIF-8 has a high specific surface area and porosity, which can effectively load and protect active ingredients such as PQQ, and regulate the slow release of active ingredients through its structural characteristics, enhancing the continuous effect of toothpaste.

[0043] β-cyclodextrin:

[0044] β-cyclodextrin, as a molecular carrier, can encapsulate and protect active substances such as PQQ, enhancing its stability in toothpaste.

[0045] β-cyclodextrin encapsulates the active ingredient PQQ through its cyclic structure, enabling it to exist stably in toothpaste and controlling its release rate to avoid premature release of the active ingredient, thereby prolonging the effect.

[0046] Chitosan:

[0047] Chitosan is a natural polysaccharide with good biodegradability and adhesiveness, capable of forming a thin film protective layer in the oral cavity.

[0048] The biodegradability and adhesiveness of chitosan enable it to form a protective film in the oral cavity, helping to repair damaged oral mucosa and providing antibacterial effects. In addition, it can also enhance the stability of other ingredients and maintain the activity of toothpaste.

[0049] Polyglutamic acid:

[0050] As a natural biodegradable polymer, polyglutamic acid has good moisture retention properties and can form a nano-composite system with chitosan.

[0051] The nano-composite system formed by the combination of polyglutamic acid and chitosan can significantly improve the lubricity of toothpaste and enhance the moisturizing effect in the oral cavity. It can also help to enhance the sustained release effect of other ingredients in toothpaste, enabling the active ingredients to exert their effects persistently.

[0052] Preferably, the particle size range of the calcium hydrogen phosphate is 2 - 10 microns; glycerol is used as a humectant; sodium dodecyl sulfate is used as a surfactant; carboxymethyl cellulose is used as a thickener, and its viscosity range is 500 - 2000 mPa·s; the sweeteners include xylitol and erythritol, and the two are mixed in a mass ratio of 1:1 - 3:1; mint essence is used as a flavoring agent; sodium benzoate is used as a preservative; the molar ratio of magnesium to aluminum in the LDH loaded with pyrroloquinoline quinone complex is controlled at 2:1 - 4:1, the loading amount of pyrroloquinoline quinone is controlled at 10 - 50 wt%, and ultrasonic-assisted dispersion is adopted; the molar ratio of β-cyclodextrin to pyrroloquinoline quinone is controlled at 1:1 - 2:1.

[0053] Preferably, the honeysuckle extract, forsythia extract, tangerine peel extract, schisandra chinensis extract, lophatherum gracile extract, isatis root extract and licorice extract are used as antibacterial, anti-inflammatory, antioxidant and oral care active ingredients; the average particle size range of ZIF-8 particles is 50-200 nanometers, the specific surface area is between 500-1500 square meters per gram, and it degrades in an acidic environment with a pH below 5.5; the molecular weight range of chitosan is 50-200 kDa, and the degree of deacetylation is controlled at 80-95%; the molecular weight of polyglutamic acid is 100-500 kDa, forming a nano composite system with chitosan with a ζ potential of -20 mV to -40 mV.

[0054] The present invention also provides a PQQ herbal toothpaste process for oral mucosa protection and repair, comprising the following steps:

[0055] S1. Dissolve magnesium nitrate and aluminum nitrate in deionized water, stir evenly, slowly add sodium hydroxide solution, adjust the pH to 9.5, continuously stir until the reaction is complete, let it stand and then centrifuge, discard the supernatant, wash and perform ultrasonic treatment to obtain a layered double hydroxide complex loaded with pyrroloquinoline quinone;

[0056] S2. Mix the layered double hydroxide complex obtained in step S1 with zinc nitrate solution, ultrasonically disperse it, slowly add 2-methylimidazole solution, control the pH to 8.5, stir until the reaction is complete, let it stand and then centrifuge, wash and dry to obtain a metal-organic framework loaded with pyrroloquinoline quinone complex;

[0057] S3. Dissolve chitosan in acetic acid solution, dissolve polyglutamic acid in deionized water, mix them, and slowly add the polyglutamic acid solution to the chitosan solution, stir evenly, perform ultrasonic treatment and then let it stand to obtain a chitosan-polyglutamic acid nano complex;

[0058] S4. Heat deionized water to 70°C, add carboxymethyl cellulose, glycerol, sodium lauryl sulfate, sodium benzoate, xylitol and erythritol, stir evenly to form a stable gel for the matrix;

[0059] S5. Mix the metal-organic framework loaded with pyrroloquinoline quinone complex obtained in step S2 with the chitosan-polyglutamic acid nano complex obtained in step S3, ultrasonically disperse it, and then add honeysuckle extract, forsythia extract, tangerine peel extract, schisandra chinensis extract, lophatherum gracile extract, isatis root extract and licorice extract, stir evenly to make them evenly distributed;

[0060] S6. Add calcium hydrogen phosphate to the mixture obtained in step S5, stir evenly to make the matrix evenly dispersed, adjust the pH to 7.0, then add mint essence, stir well, cool to 25°C, and perform low-temperature homogenization stirring to obtain a stable PQQ herbal toothpaste.

[0061] Preferably, in step S1, 0.2 mol of magnesium nitrate and 0.1 mol of aluminum nitrate are weighed and dissolved in deionized water, and continuously stirred for 30 min under the conditions of a stirring speed of 700 rpm and a stirring temperature of 30 °C;

[0062] Under the stirring state, 200 mL of sodium hydroxide solution with a concentration of 2 mol / L is added to stabilize the pH value of the solution at 9.5 and continuously stirred for 2 h;

[0063] After the stirring is completed, the solution is allowed to stand and precipitate for 30 min, then centrifuged at a centrifugation speed of 6000 rpm for 20 min, the supernatant is discarded, and the precipitate is washed three times with deionized water;

[0064] The obtained precipitate is redispersed in deionized water, pyrroloquinoline quinone solution is added, and treated with an ultrasonic power of 400 W for 10 min;

[0065] Subsequently, continue to stir for 2 h under the condition of a stirring speed of 700 rpm; then centrifuge at a centrifugation speed of 6000 rpm for 15 min, collect the obtained solid, and dry it at 60 °C for 12 h to obtain a layered double hydroxide supported pyrroloquinoline quinone complex.

[0066] Preferably, in step S2, 0.15 mol of zinc nitrate is weighed and dissolved in deionized water, stirred at 800 rpm and a temperature of 25 °C for 20 min;

[0067] Add the layered double hydroxide supported pyrroloquinoline quinone complex obtained in step S1, disperse it with an ultrasonic power of 400 W for 10 min to make it uniformly suspended;

[0068] Subsequently, under the state of continuous stirring at 900 rpm, slowly dropwise add 0.3 mol of 2-methylimidazole solution and adjust the pH value to 8.5, continuously stir for 5 h to cause a coordination reaction between 2-methylimidazole and zinc ions to form a metal-organic framework structure;

[0069] After the stirring is completed, let the solution stand for 12 h, then centrifuge at a centrifugation speed of 7000 rpm for 15 min, wash it three times with deionized water, and finally collect the precipitate and dry it at 60 °C for 24 h to obtain a metal-organic framework supported pyrroloquinoline quinone complex.

[0070] Preferably, in step S3, chitosan is weighed and dissolved in 100 mL of acetic acid solution with a pH of 5.5, and continuously stirred for 40 min under the conditions of a stirring speed of 600 rpm and a temperature of 25 °C to completely dissolve chitosan to form a uniform solution;

[0071] Weigh polyglutamic acid, dissolve it in deionized water, and continuously stir for 30 min under the conditions of a stirring speed of 700 rpm and a temperature of 25 °C;

[0072] Slowly drip the polyglutamic acid solution into the chitosan solution, and continuously stir for 60 min under the condition of a stirring speed of 800 rpm to form a uniform nano - composite of the two;

[0073] Subsequently, treat it with an ultrasonic power of 300 W for 15 min, and then let it stand for 2 h for standby.

[0074] Preferably, in step S4, weigh deionized water and heat it to 70 °C;

[0075] Add carboxymethyl cellulose and stir for 40 min under the condition of a stirring speed of 900 rpm to make it fully swell and form a stable gel - like toothpaste matrix;

[0076] Add glycerol, sodium lauryl sulfate, sodium benzoate, xylitol, and erythritol in sequence, and stir for 60 min under the condition of a stirring speed of 1000 rpm.

[0077] Preferably, in step S5, mix the metal - organic framework - loaded pyrroloquinoline quinone complex with the chitosan - polyglutamic acid nano - composite, and treat it with an ultrasonic power of 500 W for 10 min to make it fully disperse and uniformly mix;

[0078] Then slowly drip it into the toothpaste matrix prepared in step S4, and stir for 30 min under the condition of a stirring speed of 1200 rpm to make the active ingredients evenly distributed;

[0079] Subsequently, add honeysuckle extract, forsythia extract, tangerine peel extract, schisandra chinensis extract, lophatherum gracile extract, isatis root extract, and licorice extract in sequence, and stir for 40 min under the condition of a stirring speed of 900 rpm.

[0080] Preferably, in step S6, add calcium hydrogen phosphate and continuously stir for 60 min under the condition of a stirring speed of 1000 rpm to make it fully disperse and uniformly distribute;

[0081] Subsequently, adjust the pH value to 7.0, add mint essence, and stir for 30 min under the condition of a stirring speed of 800 rpm to make the essence evenly mixed;

[0082] Finally, cool it to 25 °C, and continuously stir for 30 min under the condition of low - temperature homogenization stirring at 700 rpm to make the finished product more uniform and stable, and finally obtain the PQQ herbal toothpaste.

[0083] The present invention provides a PQQ herbal toothpaste for oral mucosa protection and repair and its process. It has the following beneficial effects:

[0084] 1. The present invention adopts the technical solution of combining calcium hydrogen phosphate and glycerol, achieving the improvement of the viscosity and lubricity of toothpaste, while enhancing the cleaning effect of toothpaste. Compared with the prior art that only uses a single thickening agent or lubricating component, the present invention effectively avoids the problems of overly thin toothpaste texture or discomfort during use, ensuring a good user experience.

[0085] 2. By using pyrroloquinoline quinone (PQQ) - loaded layered double hydroxide (LDH) composite in the present invention, PQQ can be continuously released in the oral cavity, enhancing the antioxidant and oral repair functions of toothpaste. Compared with traditional oral care products, the present invention solves the problem of too fast release of active ingredients, effectively prolonging its repair effect on the oral cavity.

[0086] 3. The present invention uses plant extracts, such as honeysuckle, forsythia, and tangerine peel, as active ingredients, which can achieve strong antibacterial, anti - inflammatory, and antioxidant functions. Compared with the prior art that only relies on chemically synthesized antibacterial components, the application of natural plant extracts in the present invention greatly reduces the possible side effects on the oral cavity, improving the safety and effect of oral care.

[0087] 4. The present invention adopts the technical solution of compounding ZIF - 8 metal - organic framework material (MOF) with β - cyclodextrin, providing a more efficient embedding and slow - release mechanism for the active ingredients in toothpaste. Compared with traditional slow - release carriers, by precisely controlling the release rate, the present invention not only improves the stability of active ingredients but also can exert its effect in the oral cavity for a long time, solving the problem of non - persistent slow - release effect in traditional technologies. BRIEF DESCRIPTION OF THE DRAWINGS

[0088] Figure 1 It is the process preparation flow chart of the present invention. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0089] Next, the technical solutions in the embodiments of the present invention will be clearly and completely described in conjunction with the accompanying drawings of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all of the embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts shall fall within the protection scope of the present invention.

[0090] Please refer to Figure 1 :

[0091] Example 1:

[0092] Steps:

[0093] 1. Dissolve 0.2 mol of magnesium nitrate and 0.1 mol of aluminum nitrate in 500 mL of deionized water. After stirring for 30 minutes, slowly add 200 mL of sodium hydroxide solution with a concentration of 2 mol / L, adjust the pH value of the solution to 9.5, and continue stirring for 2 hours.

[0094] 2. After standing for precipitation for 30 minutes, centrifuge at 6000 rpm for 20 minutes, discard the supernatant, and wash the precipitate 3 times with deionized water.

[0095] 3. Redisperse the precipitate in 200 mL of deionized water, add 0.05 mol of pyrroloquinoline quinone solution, treat it with an ultrasonic power of 400 W for 10 minutes, stir for 2 hours, centrifuge, and dry for 12 hours to obtain a layered double hydroxide composite loaded with pyrroloquinoline quinone.

[0096] 4. Dissolve 0.15 mol of zinc nitrate in 300 mL of deionized water, stir for 20 minutes, add the composite obtained in step 3, after ultrasonic dispersion for 10 minutes, slowly dropwise add 2-methylimidazole solution, adjust the pH to 8.5, stir for 5 hours, stand for precipitation for 12 hours, then centrifuge, wash, and dry for 24 hours to obtain a metal-organic framework loaded with pyrroloquinoline quinone composite.

[0097] 5. Dissolve 0.2 g of chitosan in acetic acid solution, dissolve 0.2 g of polyglutamic acid in deionized water, dropwise add the polyglutamic acid solution to the chitosan solution, stir evenly and then ultrasonically treat for 15 minutes, stand for 2 hours to obtain a nanocomposite.

[0098] 6. Heat 30 g of deionized water to 70 °C, add 1 g of carboxymethyl cellulose, 20 g of glycerol, 2 g of sodium dodecyl sulfate, 0.1 g of sodium benzoate, 0.2 g of xylitol, and 0.2 g of erythritol, stir until uniform to obtain a stable gel.

[0099] 7. Mix the metal-organic framework composite obtained in step 4 with the nanocomposite obtained in step 5, ultrasonically disperse for 10 minutes, add 0.05 g each of honeysuckle extract, forsythia extract, tangerine peel extract, schisandra chinensis extract, lophatherum gracile extract, isatis root extract, and licorice extract, and stir for 40 minutes.

[0100] 8. Add 45 g of calcium hydrogen phosphate to the mixture, stir for 60 minutes, adjust the pH to 7.0, add 1 g of mint essence, continue stirring for 30 minutes, cool to 25 °C, and perform low-temperature homogenization stirring for 30 minutes to obtain the final toothpaste.

[0101] Example 2: Differences (based on the steps of Example 1)

[0102] Based on step 4 of Example 1 (preparation of metal-organic framework composite)

[0103] In Example 1, the metal-organic framework (MOF) used was ZIF-8 (zinc-based MOF). In this example, it is changed to ZIF-67 (cobalt-based MOF) to increase the loading amount of PQQ in the framework and enhance the antioxidant effect.

[0104] Specifically, 0.15 mol of cobalt nitrate was dissolved in 300 mL of deionized water to replace the zinc nitrate solution in Example 1, and the subsequent steps remained unchanged.

[0105] Based on Step 5 of Example 1 (preparation of the nanocomposite)

[0106] The ratio of chitosan to polyglutamic acid was adjusted from 0.2 g:0.2 g to 0.3 g:0.1 g to optimize the stability of the nanocomposite and improve its dispersibility in the toothpaste system.

[0107] The remaining steps remained the same.

[0108] Based on Step 6 of Example 1 (preparation of the gel matrix)

[0109] The sweetener combination was adjusted: in Example 1, the ratio of xylitol and erythritol was 0.2 g each. In this example, it was adjusted to 0.2 g of xylitol and 0.1 g of erythritol to optimize the sweetness and long-lasting freshness of the toothpaste.

[0110] The remaining ingredients and steps remained unchanged.

[0111] Based on Step 7 of Example 1 (addition of the plant extract)

[0112] In terms of the plant extract combination, in Example 1, honeysuckle, forsythia, tangerine peel, schisandra chinensis, lophatherum gracile, isatis root, and licorice were used. In this example, the schisandra chinensis extract was removed and 0.05 g of dandelion extract was added to enhance the antibacterial and anti-inflammatory effects and improve the oral repair effect.

[0113] The other extracts and addition methods remained unchanged.

[0114] Based on Step 8 of Example 1 (preparation of the final product)

[0115] The ratio of the mineral filler was adjusted:

[0116] Calcium hydrogen phosphate was reduced to 43 g (45 g in Example 1).

[0117] 2 g of fluorapatite was added to enhance the enamel repair ability and improve the anti-caries effect.

[0118] The other steps remained the same.

[0119] Example 3: Differences (based on the steps of Example 1)

[0120] Based on Step 3 of Example 1 (Preparation of LDH Loaded with PQQ Complex)

[0121] Replace MgAl-LDH (magnesium-aluminum layered double hydroxide) with NiAl-LDH (nickel-aluminum layered double hydroxide) to improve the stability and sustained-release effect of PQQ in the oral environment, make the release of active ingredients more uniform, and extend the action time.

[0122] Specifically, dissolve 0.2 mol of nickel nitrate and 0.1 mol of aluminum nitrate in 500 mL of deionized water, and keep the subsequent operation steps unchanged.

[0123] Based on Step 5 of Example 1 (Preparation of Nanocomposite)

[0124] Replace 0.2 g of polyglutamic acid with 0.2 g of hyaluronic acid to enhance the moisturizing effect of the toothpaste, improve oral adhesiveness, and reduce the discomfort of oral dryness.

[0125] The remaining preparation steps remain unchanged.

[0126] Based on Step 6 of Example 1 (Preparation of Gel Matrix)

[0127] Improve the gel matrix to enhance consistency and stability:

[0128] Remove carboxymethyl cellulose (1 g), and replace it with 0.5 g of xanthan gum and 0.5 g of guar gum to enhance the colloidal network structure, make the toothpaste more rheological, and improve the usage experience.

[0129] Other matrix components and heating methods remain unchanged.

[0130] Based on Step 7 of Example 1 (Addition of Plant Extract)

[0131] Optimization of plant extract:

[0132] Remove the isatis root extract to reduce possible bitterness and improve the usage comfort.

[0133] Add green tea extract (0.05 g) and rosemary extract (0.05 g) to enhance the antioxidant performance and further improve the oral freshness effect.

[0134] The types and addition methods of the remaining extracts remain unchanged.

[0135] Based on Step 8 of Example 1 (Formulation of Final Product)

[0136] Adjustment of mineral filler:

[0137] Reduce calcium hydrogen phosphate to 42 g (45 g in Example 1).

[0138] Add 3g of nano-hydroxyapatite, which can effectively fill the micro-damage of tooth enamel, improve the anti-caries and anti-sensitivity effects, and enhance the remineralization ability of teeth.

[0139] Other steps such as stirring, homogenizing, cooling, etc. remain unchanged.

[0140] Comparative Example 1 (Based on Example 1, removing the LDH-loaded PQQ complex)

[0141] Comparison objective: Verify the role of the LDH-loaded PQQ complex, observe its effect on the release of active ingredients, and investigate its effect on improving the stability of ingredients and prolonging the action time.

[0142] Preparation process: Step 3 (preparation of the LDH-loaded PQQ complex) is omitted, that is, MgAl-LDH is not used to load PQQ.

[0143] Direct addition of PQQ: Dissolve 0.05 mol of PQQ directly in 200 mL of deionized water, and without LDH complexation, directly add it to the toothpaste system.

[0144] Step 4 (preparation of the metal-organic framework complex) and the remaining steps are the same as those in Example 1, including the preparation of the nano-complex, the preparation of the gel matrix, the addition of the plant extract, and the final formulation, etc.

[0145] Comparative Example 2 (Based on Example 2, using ordinary ZIF-8 instead of ZIF-67)

[0146] Comparison objective: Investigate the effects of ZIF-67 (cobalt-based MOF) compared to ZIF-8 (zinc-based MOF) on the PQQ loading capacity, stability, and slow-release performance, and analyze its contribution to the antioxidant effect.

[0147] Preparation process: Step 4 (preparation of the metal-organic framework complex) is changed to use ZIF-8 instead of ZIF-67:

[0148] Dissolve 0.15 mol of zinc nitrate (replacing cobalt nitrate in Example 2) in 300 mL of deionized water and stir for 20 minutes.

[0149] Dropwise add the 2-methylimidazole solution, adjust the pH to 8.5, stir for 5 hours, let it stand for precipitation, centrifuge, wash, and dry to obtain the ZIF-8-loaded PQQ complex.

[0150] The remaining steps are the same as those in Example 2, including the preparation of the nano-complex, the addition of the plant extract, the final formulation, etc.

[0151] Comparative Example 3 (Based on Example 3, removing hyaluronic acid and using the traditional humectant glycerol)

[0152] Comparison objective: To verify the moisturizing effect of hyaluronic acid in toothpaste, analyze its impact on improving oral moisture and reducing dry mouth, and compare the effects with those of the traditional moisturizer glycerol.

[0153] Preparation process: Step 5 (preparation of nanocomposite): Remove 0.2 g of hyaluronic acid and replace it with an additional 0.2 g of glycerol, and keep the other steps unchanged.

[0154] Step 6 (preparation of gel matrix): Remove 0.5 g of xanthan gum + 0.5 g of guar gum and change it back to 1 g of carboxymethyl cellulose to simulate the traditional thickener system.

[0155] All other steps are the same as in Example 3, including LDH loading, MOF composite, plant extract, and final formulation.

[0156] Experiment 1: Experiment to verify the effect of LDH-loaded PQQ composite

[0157] Experiment description

[0158] Experiment purpose:

[0159] This experiment is mainly used to verify the effect of LDH-loaded PQQ composite in the toothpaste system, especially its impact on the stability of active ingredients, sustained-release effect, and oral care performance.

[0160] Experiment steps:

[0161] Sample preparation

[0162] Prepare toothpaste samples using the formulation of Example 1, including LDH-loaded PQQ composite (experimental group).

[0163] Prepare control samples using the formulation of Comparative Example 1, where PQQ is directly added to the toothpaste system without LDH loading (control group).

[0164] Stability test

[0165] Store the two groups of samples in three environments of 25 °C, 40 °C, and 4 °C respectively, and detect the content change of PQQ after 1 week, 2 weeks, 4 weeks, and 8 weeks, and determine it by high performance liquid chromatography (HPLC).

[0166] Sustained-release test

[0167] Use an artificial saliva buffer system (pH 6.8) to simulate the oral environment, and test the PQQ release curves of the two groups of samples within 1 h, 4 h, 12 h, and 24 h respectively, and measure the release amount using an ultraviolet-visible spectrophotometer.

[0168] Antioxidant capacity test

[0169] The antioxidant capacity of the sample was evaluated using the DPPH free radical scavenging experiment. Equal amounts of toothpaste solution were taken, and DPPH solution (concentration 0.1 mmol / L) was added. After reacting for 30 min, the absorbance change at 517 nm was measured, and the free radical scavenging rate was calculated.

[0170] Oral care effect test

[0171] Fifty subjects were selected and used the toothpaste of the experimental group and the control group respectively, once in the morning and once in the evening every day for 4 consecutive weeks. Subjective feedback such as oral moisture, improvement of gingival inflammation, and change of breath were recorded, and data analysis was carried out in combination with oral pH measurement.

[0172] The experimental data are shown in the following table:

[0173] Table 1: Influence of LDH-loaded PQQ complex on the stability of PQQ

[0174]

[0175] Table 2: Influence of LDH-loaded PQQ complex on the sustained-release performance of PQQ

[0176] Release time Experimental group (%) Control group (%) 1h 8.5 25.3 4h 18.2 42.7 12h 41.3 68.9 24h 73.4 89.2

[0177] Table 3: DPPH free radical scavenging rate (antioxidant capacity)

[0178] Group DPPH scavenging rate (%) Experimental group 81.3 Control group 55.8

[0179] Experimental summary

[0180] The stability of the LDH-loaded PQQ complex showed great advantages in the experiment. In the control group where PQQ was directly dissolved, with the passage of time, its active ingredients decreased rapidly. Especially under the high temperature condition of 40 °C, after only 8 weeks, the PQQ content dropped to 41.7%. In contrast, the PQQ in the experimental group remained above 80.2% under the same conditions (see Table 1). This indicates that the LDH structure isolates PQQ from the external environment to a certain extent, reduces the rate of oxidative degradation, and thus improves the long-term stability of the active ingredient.

[0181] In the sustained-release experiment, in the control group where PQQ was directly added, 42.7% was released within just 4 h, while the experimental group only released 18.2% in the same time, and gradually released to 73.4% within 24 h (see Table 2). This difference is difficult to explain by simple physical mixing. It is more likely that the PQQ loaded on LDH is affected by the interlayer force and gradually releases into the oral environment, making the bioavailability more persistent. This also means that the PQQ in the toothpaste can play a role for a longer time, rather than being washed away by saliva in a short time, enhancing the tooth protection effect in actual use.

[0182] The results of the antioxidant capacity test are also worthy of attention. The DPPH scavenging rate of the experimental group was as high as 81.3%, far higher than that of the control group at 55.8% (see Table 3). This may be directly related to the release rate of PQQ. Encapsulated by the LDH structure, the molecular structure of PQQ is more stable, and the rate of reactive oxygen species consumption is lower. Therefore, under long-term action, it can still maintain a high antioxidant capacity. This also conforms to the oral care feedback of the subjects. The people using the toothpaste of the experimental group generally reported an improvement in oral moisture and a more obvious remission of gum inflammation.

[0183] Experiment 2: Oral Care Effect and Stability Test of ZIF-67 Loaded with PQQ Complex

[0184] Experiment Description

[0185] Experiment Purpose:

[0186] The purpose of this experiment is to verify the antioxidant capacity, stability and slow release effect in toothpaste of the ZIF-67 (cobalt-based MOF) loaded with PQQ complex, and compare it with the traditional ZIF-8 (zinc-based MOF).

[0187] Experiment Steps:

[0188] Sample Preparation

[0189] Prepare toothpaste samples using the ZIF-67 loaded with PQQ complex.

[0190] Prepare another ZIF-8 loaded with PQQ complex as the control group with the same other formulations.

[0191] PQQ Stability Test

[0192] Store the two groups of samples in three environments of 25°C, 40°C and 4°C respectively, and measure the changes in PQQ content after 1 week, 2 weeks, 4 weeks and 8 weeks.

[0193] Determine the PQQ content in the samples using high performance liquid chromatography (HPLC).

[0194] Slow Release Test

[0195] In a simulated oral environment, use an artificial saliva buffer solution (pH 6.8) to test the release of PQQ in the samples.

[0196] Record the PQQ release amounts of the samples within 1h, 4h, 12h and 24h, and measure the absorbance changes using an ultraviolet-visible spectrophotometer.

[0197] Antioxidant Capacity Test

[0198] Use the DPPH free radical scavenging experiment to detect the antioxidant capacity of the two groups of samples.

[0199] Take a quantitative amount of toothpaste solution for each group, add DPPH solution, measure the absorbance change at 517 nm after 30 minutes, and calculate the free radical scavenging rate.

[0200] Oral care effect test

[0201] Select 60 subjects, and each group uses the experimental group and control group toothpaste respectively, twice a day for 4 consecutive weeks.

[0202] Through subjective questionnaires and oral endoscopy examinations, record subjective and objective effects such as oral moisture, improvement of bad breath, and gingival inflammation.

[0203] The experimental data are shown in the following table:

[0204] Table 1: Effect of ZIF-67 loaded with PQQ complex on the stability of PQQ

[0205]

[0206] Table 2: Effect of ZIF-67 loaded with PQQ complex on the sustained release performance of PQQ

[0207] Release time Experimental group (%) Control group (%) 1h 9.2 22.1 4h 17.3 35.4 12h 33.7 59.8 24h 69.1 85.6

[0208] Table 3: Antioxidant capacity test data

[0209] Group DPPH scavenging rate (%) Experimental group 84.7 Control group 60.2

[0210] Experimental summary

[0211] The stability of the ZIF-67 loaded with PQQ complex has a significant advantage over the ZIF-8 loaded with PQQ complex. According to the data in Table 1, the stability of the experimental group in a high-temperature environment of 40 °C is significantly better than that of the control group. Especially after 8 weeks, the PQQ content in the experimental group remains at 81.7%, while that in the control group drops to only 49.5%. This indicates that as a cobalt-based metal-organic framework, ZIF-67 may enhance its stability and anti-degradation ability in a thermal environment through metal-ligand interactions with PQQ molecules.

[0212] In the sustained release performance test, the release curve of the ZIF-67 loaded with PQQ complex also shows better results than that of ZIF-8. As can be seen from Table 2, the release amount of the experimental group within 1 h is 9.2%, which is significantly lower than 22.1% of the control group. This indicates that ZIF-67 has a stronger encapsulation effect on PQQ, resulting in a slower release and enabling a more sustained release of PQQ, thereby improving the long-term effectiveness of oral care.

[0213] The antioxidant capacity test further confirmed that PQQ loaded on ZIF-67 had a stronger antioxidant effect. The DPPH scavenging rate of the experimental group was 84.7%, far exceeding that of the control group (60.2%) (see Table 3). This advantage may be related to the framework structure of ZIF-67 and its loading capacity. During the slow release process, PQQ can maintain its antioxidant activity for a longer time, providing long-term protection for oral health.

[0214] Experiment 3: Moisturizing and Repairing Effect Test of Hyaluronic Acid in Toothpaste

[0215] Experiment Description

[0216] Experiment Purpose:

[0217] This experiment aimed to study the moisturizing and repairing effects of hyaluronic acid in toothpaste, especially its effects on reducing oral dryness and improving gum health, and to compare it with the traditional moisturizer glycerol.

[0218] Experiment Steps:

[0219] Sample Preparation

[0220] Prepare the experimental group toothpaste containing hyaluronic acid (0.2 g), and the remaining ingredients are the same as in Example 3.

[0221] Prepare the control group toothpaste, replacing hyaluronic acid with an equal amount of glycerol (0.2 g), and the remaining ingredients are the same as in the experimental group.

[0222] Oral Moisture Test

[0223] Select 40 subjects and use the experimental group and control group toothpastes respectively, once in the morning and once in the evening every day for 4 consecutive weeks.

[0224] Use an oral moisture sensor to measure the humidity change in the oral cavity, record the daily measurement data, and evaluate the moisturizing effect.

[0225] Gum Inflammation Improvement Test

[0226] After each subject uses the toothpaste, record the degree of gum inflammation (based on the Loe-Silness index) and take a photo of the gums to evaluate the reduction of inflammation.

[0227] Use an oral endoscope to observe the changes in the inflamed area. After 4 consecutive weeks of use, re-evaluate and record the data.

[0228] Bad Breath Improvement Test

[0229] After each subject uses the toothpaste, measure the bad breath concentration with a bad breath tester to evaluate the change in bad breath freshness.

[0230] Measure the changes after 2 weeks and 4 weeks of use.

[0231] Skin repair test

[0232] The experimental group of toothpaste using hyaluronic acid was tested for repair on the skin around the mouth, and the skin moisture and repair effect were observed. Data were recorded weekly for 4 consecutive weeks.

[0233] The experimental data are shown in the following table:

[0234] Table 1: Effects of hyaluronic acid and glycerol on oral moisture

[0235] Usage time Experimental group (humidity %) Control group (humidity %) 1 week 72.3 59.1 2 weeks 75.8 62.4 3 weeks 79.5 65.2 4 weeks 82.1 68.3

[0236] Table 2: Effects of hyaluronic acid on improving gingival inflammation

[0237] Usage time Experimental group (improvement of inflammation %) Control group (improvement of inflammation %) 1 week 13.4 8.1 2 weeks 21.2 13.6 3 weeks 29.9 19.3 4 weeks 37.5 24.8

[0238] Table 3: Improvement of fresh breath

[0239] Usage time Experimental group (freshness of breath %) Control group (freshness of breath %) 2 weeks 40.1 30.2 4 weeks 55.6 43.9

[0240] Experimental summary

[0241] The moisturizing effect of hyaluronic acid in toothpaste is quite prominent. According to the data in Table 1, the oral moisture of the experimental group reached 72.3% after one week of use and 82.1% after four weeks, far higher than 68.3% of the control group. This effect may be related to the high hydrophilicity of hyaluronic acid, which can quickly adsorb moisture and keep it in the mouth, thus enhancing the sense of oral moisture. In contrast, the effect of glycerol is relatively weak. Although it also has a certain moisturizing effect, it fails to reach the level of hyaluronic acid.

[0242] For the improvement of gingival inflammation, the effect of hyaluronic acid is also more significantly superior. Table 2 shows that the improvement of inflammation in the experimental group reached 37.5% after four weeks, while that of the control group was only 24.8%. This may be related to the repair characteristics of hyaluronic acid. It can not only increase the oral moisture, but also promote the repair and anti-inflammatory effect of soft tissues. This effect is more significant than that of glycerol, indicating that hyaluronic acid has a stronger effect in anti-inflammation.

[0243] In terms of breath improvement, the effect of the experimental group was also better than that of the control group. The breath freshness of the experimental group was 40.1% and 55.6% respectively two weeks and four weeks later, while that of the control group was only 30.2% and 43.9% (see Table 3). This may be related to the moisturizing effect of hyaluronic acid combined with the improvement of the oral environment. By keeping the mouth moist, it helps to reduce bad breath caused by dry mouth. In addition, the repair effect of hyaluronic acid on the skin around the mouth is also quite remarkable. After continuous use, the skin repair rate gradually increases to 21.4%, indicating that the application of hyaluronic acid in toothpaste is not only for moisturizing in the oral cavity, but also has a significant effect on the repair of the external skin.

[0244] Although the embodiments of the present invention have been shown and described, it will be understood by those of ordinary skill in the art that various changes, modifications, substitutions and variations can be made to these embodiments without departing from the principles and spirit of the present invention, and the scope of the present invention is defined by the appended claims and their equivalents.

Claims

1. A PQQ herbal toothpaste for oral mucosa protection and repair, characterized in that, The toothpaste comprises the following components in parts by mass: calcium hydrogen phosphate: 40 - 50 parts; glycerol: 15 - 25 parts; sodium dodecyl sulfate: 1 - 3 parts; carboxymethyl cellulose: 0.5 - 2 parts; sweetener: 0.1 - 0.5 parts; mint essence: 0.5 - 1.5 parts; sodium benzoate: 0.05 - 0.2 parts; pyrroloquinoline quinone: 0.02 - 0.1 parts; honeysuckle extract: 0.02 - 0.1 parts; forsythia extract: 0.02 - 0.1 parts; tangerine peel extract: 0.02 - 0.1 parts; schisandra chinensis extract: 0.02 - 0.1 parts; lophatherum gracile extract: 0.02 - 0.1 parts; isatis root extract: 0.02 - 0.1 parts; licorice extract: 0.02 - 0.1 parts; deionized water: 25 - 35 parts; LDH - loaded PQQ complex: 0.1 - 0.5 parts; ZIF - 8: 0.1 - 0.3 parts; β - cyclodextrin: 0.05 - 0.2 parts; chitosan: 0.05 - 0.3 parts; polyglutamic acid: 0.05 - 0.3 parts.

2. The PQQ herbal toothpaste for oral mucosa protection and repair according to claim 1, wherein The particle size range of the calcium hydrogen phosphate is 2 - 10 microns; glycerol is used as a wetting agent; sodium dodecyl sulfate is used as a surfactant; carboxymethyl cellulose is used as a thickener, and its viscosity range is 500 - 2000 mPa·s; the sweetener includes xylitol and erythritol, and the two are mixed in a mass ratio of 1:1 - 3:1; mint essence is used as a flavoring agent; sodium benzoate is used as a preservative; the molar ratio of magnesium to aluminum of the LDH - loaded pyrroloquinoline quinone complex is controlled at 2:1 - 4:1, and the loading amount of pyrroloquinoline quinone is controlled at 10 - 50 wt%, and ultrasonic - assisted dispersion is adopted; the molar ratio of β - cyclodextrin to pyrroloquinoline quinone is controlled at 1:1 - 2:

1.

3. The PQQ herbal toothpaste for oral mucosa protection and repair according to claim 1, characterized in that, The honeysuckle extract, forsythia extract, tangerine peel extract, schisandra chinensis extract, lophatherum gracile extract, isatis root extract and licorice extract are used as antibacterial, anti - inflammatory, antioxidant and oral care active ingredients; the average particle size range of the ZIF - 8 particles is 50 - 200 nanometers, the specific surface area is between 500 - 1500 square meters per gram, and it degrades in an acidic environment with a pH below 5.5; the molecular weight range of chitosan is 50 - 200 kDa, and the degree of deacetylation is controlled at 80 - 95%; the molecular weight of polyglutamic acid is 100 - 500 kDa, and it forms a nano - composite system with chitosan with a ζ - potential of - 20 mV to - 40 mV.

4. A PQQ herbal toothpaste process for oral mucosa protection and repair, applied to the PQQ herbal toothpaste for oral mucosa protection and repair according to any one of claims 1-3, characterized in that, It includes the following steps: S1. Dissolve magnesium nitrate and aluminum nitrate in deionized water, stir evenly, then slowly add sodium hydroxide solution, adjust the pH to 9.5, continuously stir until the reaction is complete, let it stand and then centrifuge, discard the supernatant, wash and perform ultrasonic treatment to obtain a layered double - hydroxide complex loaded with pyrroloquinoline quinone; S2. Mix the layered double - hydroxide complex obtained in step S1 with zinc nitrate solution, perform ultrasonic dispersion, then slowly add 2 - methylimidazole solution, control the pH at 8.5, stir until the reaction is complete, let it stand and then centrifuge, wash and dry to obtain a metal - organic framework - loaded pyrroloquinoline quinone complex; S3, dissolving chitosan in acetic acid solution, dissolving polyglutamic acid in deionized water, mixing, slowly adding polyglutamic acid solution to the chitosan solution, stirring evenly, and allowing to stand after ultrasonic treatment to obtain a chitosan-polyglutamic acid nanocomposite; S4, heating deionized water to 70° C., adding carboxymethyl cellulose, glycerol, sodium lauryl sulfate, sodium benzoate, xylitol and erythritol, and stirring evenly to allow the matrix to form a stable gel; S5, mixing the metal organic framework loaded pyrroloquinoline quinone complex obtained in step S2 with the chitosan-polyglutamic acid nanocomposite obtained in step S3, and adding honeysuckle extract, forsythia extract, tangerine peel extract, schisandra chinensis extract, loquat leaf extract, isatis indigotica extract and liquorice extract after ultrasonic dispersion, and stirring evenly to make them evenly distributed; S6. Add calcium hydrogen phosphate to the mixture obtained in step S5, stir evenly to evenly disperse the matrix, adjust the pH to 7.0, add mint essence, stir well, cool to 25° C., and stir homogenously at low temperature to obtain a stable PQQ herbal toothpaste.

5. A PQQ herbal toothpaste process for oral mucosa protection and repair according to claim 4, characterized in that, In step S1, 0.2 mol of magnesium nitrate and 0.1 mol of aluminum nitrate were weighed, dissolved in deionized water, and stirred for 30 min at a stirring speed of 700 rpm and a stirring temperature of 30° C.; Under stirring, add 200 mL of sodium hydroxide solution with a concentration of 2 mol / L to stabilize the pH value of the solution at 9.5, and continue stirring for 2 h; After stirring, the solution was allowed to settle for 30 min, then centrifuged at 6000 rpm for 20 min, the supernatant was discarded, and the precipitate was washed three times with deionized water; The obtained precipitate was redispersed in deionized water, pyrroloquinoline quinone solution was added, and ultrasonic treatment was performed at 400 W for 10 min; Subsequently, stirring was continued for 2 hours at a stirring speed of 700 rpm; centrifugation was then performed at a centrifugal speed of 6000 rpm for 15 minutes, the resulting solid was collected, and dried at 60° C. for 12 hours to obtain a layered double hydroxide-supported pyrroloquinoline quinone complex.

6. The process of a PQQ herbal toothpaste for oral mucosa protection and repair according to claim 4, characterized in that, In step S2, 0.15 mol of zinc nitrate was weighed and dissolved in deionized water, and stirred at 800 rpm, at a temperature of 25° C., for 20 min; Add the layered double hydroxide-supported pyrroloquinoline quinone complex described in step S1, and disperse it for 10 minutes using 400 W ultrasonic power to make it uniformly suspended; Subsequently, 0.3 mol of 2-methylimidazole solution was slowly added dropwise while stirring at 900 rpm, and the pH value was adjusted to 8.

5. The mixture was stirred for 5 h to allow 2-methylimidazole to react with zinc ions to form a metal organic framework structure. After stirring, the solution was allowed to stand for 12 h, centrifuged at 7000 rpm for 15 min, and washed three times with deionized water. Finally, the precipitate was collected and dried at 60 °C for 24 h to obtain a metal organic framework-loaded pyrroloquinoline quinone complex.

7. A PQQ herbal toothpaste process for oral mucosa protection and repair according to claim 4, characterized in that, In step S3, chitosan was weighed and dissolved in 100 mL of acetic acid solution with a pH of 5.5, and continuously stirred for 40 min under the conditions of a stirring speed of 600 rpm and a temperature of 25 °C to completely dissolve chitosan to form a homogeneous solution; Polyglutamic acid was weighed and dissolved in deionized water, and continuously stirred for 30 min under the conditions of a stirring speed of 700 rpm and a temperature of 25 °C; The polyglutamic acid solution was slowly added dropwise to the chitosan solution, and continuously stirred for 60 min under the condition of a stirring speed of 800 rpm to form a homogeneous nanocomposite of the two; Subsequently, it was treated with an ultrasonic power of 300 W for 15 min and then left standing for 2 h for standby.

8. The process of PQQ herbal toothpaste for oral mucosa protection and repair according to claim 4, characterized in that, In step S4, deionized water was weighed and heated to 70 °C; Carboxymethyl cellulose was added and stirred for 40 min under the condition of a stirring speed of 900 rpm to completely swell it to form a stable gel-like toothpaste matrix; Glycerol, sodium dodecyl sulfate, sodium benzoate, xylitol, and erythritol were added in sequence and stirred for 60 min under the condition of a stirring speed of 1000 rpm.

9. The process of PQQ herbal toothpaste for oral mucosa protection and repair according to claim 4, characterized in that, In step S5, the metal-organic framework loaded with pyrroloquinoline quinone complex was mixed with the chitosan-polyglutamic acid nanocomposite, and treated with an ultrasonic power of 500 W for 10 min to fully disperse and uniformly mix them; Then it was slowly added dropwise to the toothpaste matrix prepared in step S4 and stirred for 30 min under the condition of a stirring speed of 1200 rpm to uniformly distribute the active ingredients; Subsequently, honeysuckle extract, forsythia extract, tangerine peel extract, schisandra chinensis extract, lophatherum gracile extract, isatis root extract, and licorice extract were added in sequence and stirred for 40 min under the condition of a stirring speed of 900 rpm.

10. A PQQ herbal toothpaste process for oral mucosa protection and repair according to claim 4, characterized in that, In step S6, calcium hydrogen phosphate was added and continuously stirred for 60 min under the condition of a stirring speed of 1000 rpm to fully disperse and uniformly distribute it; Subsequently, the pH value was adjusted to 7.0, peppermint essence was added, and stirred for 30 min under the condition of a stirring speed of 800 rpm to uniformly mix the essence; Finally, it was cooled to 25 °C and continuously stirred for 30 min under the condition of low-temperature homogenization stirring at 700 rpm to make the finished product more uniform and stable, and finally obtain PQQ herbal toothpaste.

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