Composition containing mesoporous hydroxyapatite repair material and preparation method thereof

Abstract

The invention relates to a composition containing a mesoporous hydroxyapatite repairing material and a preparation method of the composition, and belongs to the technical field of dental oral care. The composition of the repairing material containing mesoporous hydroxyapatite is prepared from the following components in parts by weight: 25 to 35 parts of composite mesoporous hydroxyapatite, 5 to 10 parts of hydrated silica, 3 to 5 parts of humectant, 2 to 3 parts of calcium phosphate, 1 to 2 parts of potassium sorbate, 0.5 to 1.5 parts of lauryl sodium sulfate, 1.5 to 2.5 parts of xanthan gum, 0.6 to 0.8 part of stannous fluoride and 40 to 50 parts of deionized water. Wherein the composite mesoporous hydroxyapatite is obtained by compounding epsilon-polylysine and tea polyphenol. The composition prepared by the preparation method disclosed by the invention has good bacteriostatic and enamel repairing effects.

Description

Technical Field

[0001] The invention belongs to the technical field of dental oral care and relates to a composition containing a mesoporous hydroxyapatite repair material and a preparation method thereof. Background Art

[0002] In the oral care field, enamel damage and gum problems are common oral health issues. Tooth enamel is the hard outermost layer of tooth tissue. Once damaged, it can lead to oral diseases such as tooth sensitivity and caries. Gums are the supporting tissue surrounding the teeth, and their health directly affects the stability of the teeth and the overall health of the mouth.

[0003] Hydroxyapatite, the primary inorganic component of human bones and teeth, is widely used in bone repair materials and tooth remineralization agents due to its excellent biocompatibility and osteoconductivity. However, traditional hydroxyapatite materials suffer from defects such as low specific surface area, limited drug loading capacity, and insufficient mechanical strength. This makes it difficult to achieve synergistic antimicrobial activity and mineralization repair in oral care settings. Summary of the Invention

[0004] The object of the present invention is to provide a composition containing a mesoporous hydroxyapatite repair material and a preparation method thereof, which has good antibacterial and enamel repair effects.

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

[0006] A composition containing a mesoporous hydroxyapatite repair material, wherein the composition containing the mesoporous hydroxyapatite repair material has the following formula: in parts by weight, 25-35 parts of composite mesoporous hydroxyapatite, 5-10 parts of hydrated silica, 3-5 parts of a moisturizer, 2-3 parts of calcium phosphate, 1-2 parts of potassium sorbate, 0.5-1.5 parts of sodium lauryl sulfate, 1.5-2.5 parts of xanthan gum, 0.6-0.8 parts of stannous fluoride, and 40-50 parts of deionized water;

[0007] The composite mesoporous hydroxyapatite is obtained by compounding ε-polylysine and tea polyphenols.

[0008] As a preferred technical solution of the present invention, the preparation method of the composite mesoporous hydroxyapatite is as follows:

[0009] S2-1: Dissolve ε-polylysine in deionized water to prepare a solution with a concentration of 2-3 mg / mL, and adjust the pH of the solution to obtain solution A;

[0010] S2-2: Dispersing mesoporous hydroxyapatite in an ethanol solution containing 3-aminopropyltriethoxysilane, stirring at 450-550 rpm at 50-60°C for 20-24 hours, washing with deionized water, and drying in a vacuum drying oven at 60°C for 12-14 hours to obtain powder B;

[0011] S2-3: Powder B is added to solution A, and the mixture is stirred at 300-400 r / min at 4°C for 24 hours. Tea polyphenols are then added, and the stirring is continued for 4-6 hours. The mixture is washed with deionized water, and then freeze-dried at -40°C for 12 hours to obtain the composite mesoporous hydroxyapatite.

[0012] As a preferred technical solution of the present invention, the humectant is one or more of glycerol, sorbitol or polyethylene glycol.

[0013] As a preferred technical solution of the present invention, the pH of the solution in S2-1 is adjusted to 6.0-7.0.

[0014] As a preferred technical solution of the present invention, the mass ratio of 3-aminopropyltriethoxysilane in the ethanol solution in S2-2 is 5-7%.

[0015] As a preferred technical solution of the present invention, the mass ratio of powder B to solution A in S2-3 is (1-2):10.

[0016] As a preferred technical solution of the present invention, the amount of tea polyphenols added in S2-3 is 0.3 to 0.5 times the mass of powder B.

[0017] A method for preparing a composition containing a mesoporous hydroxyapatite repair material, wherein the specific steps of the preparation method are as follows:

[0018] S8-1: Add sodium lauryl sulfate, potassium sorbate, stannous fluoride, and a moisturizer to deionized water at 30-40°C according to the formula ratio and stir for 10-20 minutes to obtain component A;

[0019] S8-2: Add composite mesoporous hydroxyapatite and calcium phosphate to a dry powder mixer and mix at a speed of 100-200 r / min for 10-20 minutes. Then add hydrated silica, increase the speed to 200-300 r / min, and continue mixing for 5-10 minutes to obtain component B;

[0020] S8-3: Add component B to component A, stir at a speed of 700-800 r / min for 30 minutes, add xanthan gum, and homogenize for 5-10 minutes to obtain the composition containing the mesoporous hydroxyapatite repair material.

[0021] As a preferred technical solution of the present invention, the stirring speed in S8-1 is 500-600 r / min.

[0022] As a preferred technical solution of the present invention, the homogenization pressure in S8-3 is 20 to 30 MPa.

[0023] ε-Polylysine is a natural antimicrobial peptide with broad-spectrum antimicrobial activity, effectively inhibiting the growth of a variety of oral pathogens, such as bacteria and fungi. By loading it onto mesoporous hydroxyapatite, the antimicrobial component can be sustained-released, thereby prolonging the antimicrobial effect and enhancing the antimicrobial efficacy of the oral care material. Furthermore, surface modification of the mesoporous hydroxyapatite enhances its binding capacity with ε-Polylysine, further enhancing the antimicrobial effect.

[0024] Mesoporous hydroxyapatite inherently possesses excellent biocompatibility and can form a favorable bond with oral tissue. Surface amino modification with 3-aminopropyltriethoxysilane can further improve its dispersibility and interaction with other bioactive molecules. This modification not only enhances the binding ability of mesoporous hydroxyapatite with ε-polylysine but also helps improve the material's cellular affinity, promoting regeneration and repair of the oral mucosa and periodontal tissues.

[0025] Tea polyphenols are natural antioxidants with significant anti-inflammatory and antioxidant activity. When added to composite mesoporous hydroxyapatite, they can create a synergistic effect with ε-polylysine, alleviating oral inflammation and protecting oral tissues from free radical damage. This synergistic effect helps accelerate oral wound healing and enhance repair effectiveness.

[0026] The porous structure of mesoporous hydroxyapatite enables uniform loading and intelligent release of ε-polylysine and tea polyphenols. This release characteristic allows the active ingredients to exert their effects continuously and stably in the oral environment, thus ensuring the long-term effectiveness of the repair material.

[0027] Beneficial effects of the present invention:

[0028] The present composition of the mesoporous hydroxyapatite repair material, through the scientific proportions of its components and the preparation process of the composite mesoporous hydroxyapatite, achieves excellent antibacterial properties, good biocompatibility and tissue repair capabilities, and stable release of active ingredients. Furthermore, the synergistic effect of the components further enhances the overall effectiveness of the repair material. DETAILED DESCRIPTION

[0029] In order to further illustrate the technical means and effects adopted by the present invention to achieve the predetermined purpose of the invention, the specific implementation methods, structures, features and effects of the present invention are described in detail below in combination with the embodiments.

[0030] In the Examples and Comparative Examples of the present invention:

[0031] Mesoporous hydroxyapatite: purchased from Shanghai Yien Chemical Technology Co., Ltd.

[0032] Hydrated silica: purchased from Wuhan Jiyesheng Chemical Co., Ltd.

[0033] Calcium phosphate: purchased from Shanghai Dingfen Chemical Technology Co., Ltd.

[0034] Potassium sorbate: purchased from Jiangsu Duoyang Bioengineering Technology Co., Ltd.

[0035] Sodium lauryl sulfate: purchased from Hunan Lichen Aowei Industrial Co., Ltd.

[0036] Xanthan gum: purchased from Shaanxi Fujuyuan Biotechnology Co., Ltd.

[0037] Stannous fluoride: purchased from Suzhou Yingke Biotechnology Co., Ltd.

[0038] ε-Polylysine: purchased from Wuhan Fuxin Chemical Co., Ltd.

[0039] Tea polyphenols: purchased from Shaanxi Xinyanghe Biotechnology Co., Ltd.

[0040] Example 1

[0041] A composition containing a mesoporous hydroxyapatite repair material, wherein the composition having a formula 1 thereof is as follows: in parts by weight, 30 parts of composite mesoporous hydroxyapatite, 8 parts of hydrated silica, 4 parts of glycerol, 2.5 parts of calcium phosphate, 1.5 parts of potassium sorbate, 1 part of sodium lauryl sulfate, 2 parts of xanthan gum, 0.7 part of stannous fluoride, and 45 parts of deionized water;

[0042] The preparation method of the composite mesoporous hydroxyapatite is as follows:

[0043] S2-1: Dissolve ε-polylysine in deionized water to prepare a solution with a concentration of 2.5 mg / mL, and adjust the pH of the solution to 6.5 to obtain solution A;

[0044] S2-2: Mesoporous hydroxyapatite was dispersed in an ethanol solution containing 6% by mass of 3-aminopropyltriethoxysilane, stirred at 500 rpm at 55°C for 22 h, washed with deionized water, and dried in a vacuum drying oven at 60°C for 13 h to obtain powder B.

[0045] S2-3: Powder B is added to solution A with a mass ratio of powder B to solution A of 1.5:10. The mixture is stirred at 4°C and 350 r / min for 24 hours. Subsequently, 0.4 times the mass of tea polyphenols of powder B is added, and stirring is continued for 5 hours. The mixture is washed with deionized water and freeze-dried at -40°C for 12 hours to obtain the composite mesoporous hydroxyapatite.

[0046] A method for preparing a composition containing a mesoporous hydroxyapatite repair material, wherein the specific steps of the preparation method are as follows:

[0047] S8-1: Sodium lauryl sulfate, potassium sorbate, stannous fluoride, and glycerol were added to 35°C deionized water according to the proportions in Formula 1, and the mixture was stirred at 550 rpm for 15 minutes to obtain component A.

[0048] S8-2: Add composite mesoporous hydroxyapatite and calcium phosphate into a dry powder mixer and mix at a speed of 150 r / min for 15 minutes. Then add hydrated silica, increase the speed to 250 r / min, and continue mixing for 8 minutes to obtain component B;

[0049] S8-3: Component B was added to component A, and the mixture was stirred at a speed of 750 r / min for 30 min. Xanthan gum was added, and the mixture was homogenized at a pressure of 25 MPa for 8 min to obtain the composition containing the mesoporous hydroxyapatite repair material.

[0050] Example 2

[0051] A composition containing a mesoporous hydroxyapatite repair material, wherein the composition having a formula 2 containing a mesoporous hydroxyapatite repair material is as follows: in parts by weight, 25 parts of composite mesoporous hydroxyapatite, 5 parts of hydrated silica, 3 parts of sorbitol, 2 parts of calcium phosphate, 1 part of potassium sorbate, 0.5 parts of sodium lauryl sulfate, 1.5 parts of xanthan gum, 0.6 parts of stannous fluoride, and 40 parts of deionized water;

[0052] The preparation method of the composite mesoporous hydroxyapatite is as follows:

[0053] S2-1: Dissolve ε-polylysine in deionized water to prepare a solution with a concentration of 2 mg / mL, and adjust the pH of the solution to 6.0 to obtain solution A;

[0054] S2-2: Mesoporous hydroxyapatite was dispersed in an ethanol solution containing 5% by mass of 3-aminopropyltriethoxysilane, stirred at 450 rpm at 50°C for 20 h, washed with deionized water, and dried in a vacuum drying oven at 60°C for 12 h to obtain powder B.

[0055] S2-3: Powder B is added to solution A with a mass ratio of powder B to solution A of 1:10, and the mixture is stirred at 300 r / min at 4°C for 24 hours. Subsequently, 0.3 times the mass of tea polyphenols of powder B is added, and stirring is continued for 4 hours. The mixture is washed with deionized water, and then freeze-dried at -40°C for 12 hours to obtain the composite mesoporous hydroxyapatite.

[0056] A method for preparing a composition containing a mesoporous hydroxyapatite repair material, wherein the specific steps of the preparation method are as follows:

[0057] S8-1: Sodium lauryl sulfate, potassium sorbate, stannous fluoride, and sorbitol were added to 30°C deionized water according to the ratio of Formula 2, and stirred at 500 rpm for 10 min to obtain component A;

[0058] S8-2: Add composite mesoporous hydroxyapatite and calcium phosphate into a dry powder mixer and mix at a speed of 100 r / min for 10 minutes. Then add hydrated silica, increase the speed to 200 r / min, and continue mixing for 5 minutes to obtain component B;

[0059] S8-3: Component B was added to component A, and the mixture was stirred at a speed of 700 r / min for 30 minutes. Xanthan gum was added, and the mixture was homogenized at a pressure of 20 MPa for 5 minutes to obtain the composition containing the mesoporous hydroxyapatite repair material.

[0060] Example 3

[0061] A composition containing a mesoporous hydroxyapatite repair material, wherein the composition having a formula 3 containing the mesoporous hydroxyapatite repair material is as follows: in parts by weight, 35 parts of composite mesoporous hydroxyapatite, 10 parts of hydrated silica, 5 parts of polyethylene glycol, 3 parts of calcium phosphate, 2 parts of potassium sorbate, 1.5 parts of sodium lauryl sulfate, 2.5 parts of xanthan gum, 0.8 part of stannous fluoride, and 50 parts of deionized water;

[0062] The preparation method of the composite mesoporous hydroxyapatite is as follows:

[0063] S2-1: Dissolve ε-polylysine in deionized water to prepare a solution with a concentration of 3 mg / mL, and adjust the pH of the solution to 7.0 to obtain solution A;

[0064] S2-2: Mesoporous hydroxyapatite was dispersed in an ethanol solution containing 7% by mass of 3-aminopropyltriethoxysilane, stirred at 550 rpm at 60°C for 24 h, washed with deionized water, and dried in a vacuum drying oven at 60°C for 14 h to obtain powder B.

[0065] S2-3: Powder B is added to solution A with a mass ratio of powder B to solution A of 2:10, and the mixture is stirred at 400 r / min at 4°C for 24 hours. Subsequently, 0.5 times the mass of tea polyphenols of powder B is added, and stirring is continued for 6 hours. The mixture is washed with deionized water, and then freeze-dried at -40°C for 12 hours to obtain the composite mesoporous hydroxyapatite.

[0066] A method for preparing a composition containing a mesoporous hydroxyapatite repair material, wherein the specific steps of the preparation method are as follows:

[0067] S8-1: Sodium lauryl sulfate, potassium sorbate, stannous fluoride, and polyethylene glycol were added to 40°C deionized water according to the ratio of Formula 3, and stirred at 600 rpm for 20 min to obtain component A;

[0068] S8-2: Add composite mesoporous hydroxyapatite and calcium phosphate into a dry powder mixer and mix at a speed of 200 r / min for 20 minutes. Then add hydrated silica, increase the speed to 300 r / min, and continue mixing for 10 minutes to obtain component B;

[0069] S8-3: Component B was added to component A, and the mixture was stirred at a speed of 800 r / min for 30 min. Xanthan gum was added, and the mixture was homogenized at a pressure of 30 MPa for 10 min to obtain the composition containing the mesoporous hydroxyapatite repair material.

[0070] Comparative Example 1

[0071] No ε-polylysine was added during the preparation of the composite mesoporous hydroxyapatite, and the remaining steps were the same as those in Example 1.

[0072] Comparative Example 2

[0073] 3-aminopropyltriethoxysilane was not added during the preparation of the composite mesoporous hydroxyapatite, and the remaining steps were the same as those in Example 1.

[0074] Comparative Example 3

[0075] Tea polyphenols were not added during the preparation of the composite mesoporous hydroxyapatite, and the remaining steps were the same as those in Example 1.

[0076] Comparative Example 4

[0077] The mesoporous hydroxyapatite was not subjected to composite treatment, and the remaining steps were the same as those in Example 1.

[0078] Comparative Example 5

[0079] In the preparation of the composite mesoporous hydroxyapatite, microporous hydroxyapatite is used instead of mesoporous hydroxyapatite, and the remaining steps are consistent with those in Example 1.

[0080] Antibacterial performance test

[0081] The antibacterial properties of the compositions prepared in the examples and comparative examples were tested according to GB / T 21510-2008 standard, and the results are shown in the following table.

[0082] Staphylococcus aureus inhibition rate (%) Example 1 97.6 Example 2 95.9 Example 3 96.4 Comparative Example 1 38.1 Comparative Example 2 83.7 Comparative Example 3 89.2 Comparative Example 4 24.4 Comparative Example 5 67.8

[0083] Tooth enamel repair performance test

[0084] According to the laboratory method (XYJC-SOP-CE-055 in vitro bovine tooth enamel demineralization-remineralization test), the samples were tested for their enamel repair and remineralization effects.

[0085] Blank control group: tooth grinding blocks before demineralization treatment;

[0086] Negative control group: tooth grinding blocks after demineralization;

[0087] Preparation of sample group slurry: Weigh a certain amount of the sample to be tested and deionized water in a ratio of 1:1.6 (sample:water), stir with a glass rod to disperse the toothpaste, and then stir with an automatic stirrer to form a homogenous slurry for later use. The sample to be tested is the composition prepared in the example and comparative example.

[0088] Test method:

[0089] (1) Preparation of tooth grinding blocks:

[0090] The bovine tooth enamel was cut into 4mm*4mm*3mm specifications using a low-speed precision cutting machine, embedded in epoxy resin, and polished using a grinder and polisher for later use.

[0091] (2) Surface microhardness test before demineralization:

[0092] Before demineralization, the surface microhardness of the teeth was tested and the values were recorded. Teeth with similar surface microhardness were selected for testing.

[0093] (3) Demineralization treatment and surface microhardness test:

[0094] The dental block was immersed in demineralization solution and demineralized at a constant temperature of 37°C. After demineralization, its surface microhardness was tested and the values were recorded.

[0095] (4) Remineralization treatment and surface microhardness test:

[0096] Take an appropriate amount of sample and evenly apply it on the surface of demineralized bovine enamel. Place the tooth on a brush grinder for scrubbing twice a day for 2 minutes each time. During the interval, place the sample in 37°C artificial saliva and change the artificial saliva every 24 hours. Measure the surface microhardness after one week.

[0097] The demineralization solution contained: 0.1 mol / L lactic acid, 0.1 mol / L sodium hydroxide, 30 g / L hydroxymethyl cellulose, and the pH was adjusted to 4.2 with 0.1 mol / L NaOH.

[0098] Artificial saliva: Dissolve 0.78 g / L sodium dihydrogen phosphate, 0.795 g / L calcium chloride, 0.005 g / L sodium sulfide, 0.4 g / L potassium chloride, 0.4 g / L sodium chloride, and 1 g / L urea in 800 mL of deionized water, adjust the pH to 6.8, and make up to 1000 mL. The results are shown in the table below.

[0099]

[0100]

[0101] It can be seen from the data of the examples and comparative examples that the composition prepared in the present invention has the effects of repairing tooth enamel and remineralizing.

[0102] The above description is merely a preferred embodiment of the present invention and does not constitute any form of limitation to the present invention. Although the present invention has been disclosed as a preferred embodiment as above, it is not intended to limit the present invention. Any person skilled in the art can make some changes or modifications to equivalent embodiments using the technical contents disclosed above without departing from the scope of the technical solution of the present invention. However, any simple modifications, equivalent changes and modifications made to the above embodiments based on the technical essence of the present invention without departing from the content of the technical solution of the present invention are still within the scope of the technical solution of the present invention.

Claims

1. A composition containing a mesoporous hydroxyapatite repair material, characterized in that: The composition of the mesoporous hydroxyapatite repair material is formulated as follows: in parts by weight, 25-35 parts of composite mesoporous hydroxyapatite, 5-10 parts of hydrated silica, 3-5 parts of moisturizer, 2-3 parts of calcium phosphate, 1-2 parts of potassium sorbate, 0.5-1.5 parts of sodium lauryl sulfate, 1.5-2.5 parts of xanthan gum, 0.6-0.8 parts of stannous fluoride, and 40-50 parts of deionized water. The composite mesoporous hydroxyapatite is obtained by compounding ε-polylysine and tea polyphenols.

2. The composition containing mesoporous hydroxyapatite repair material according to claim 1, characterized in that: The preparation method of the composite mesoporous hydroxyapatite is as follows: S2-1: Dissolve ε-polylysine in deionized water to prepare a solution with a concentration of 2-3 mg / mL, and adjust the pH of the solution to obtain solution A; S2-2: Dispersing mesoporous hydroxyapatite in an ethanol solution containing 3-aminopropyltriethoxysilane, stirring at 450-550 rpm at 50-60°C for 20-24 hours, washing with deionized water, and drying in a vacuum drying oven at 60°C for 12-14 hours to obtain powder B; S2-3: Powder B is added to solution A, and the mixture is stirred at 300-400 r / min at 4°C for 24 hours. Tea polyphenols are then added, and the stirring is continued for 4-6 hours. The mixture is washed with deionized water, and then freeze-dried at -40°C for 12 hours to obtain the composite mesoporous hydroxyapatite.

3. The composition containing mesoporous hydroxyapatite repair material according to claim 1, characterized in that: The moisturizing agent is one or more of glycerin, sorbitol or polyethylene glycol.

4. The composition containing mesoporous hydroxyapatite repair material according to claim 2, characterized in that: In the S2-1, the pH of the solution is adjusted to 6.0-7.

0.

5. The composition containing mesoporous hydroxyapatite repair material according to claim 2, characterized in that: The mass ratio of 3-aminopropyltriethoxysilane in the ethanol solution in S2-2 is 5-7%.

6. The composition containing mesoporous hydroxyapatite repair material according to claim 2, characterized in that: The mass ratio of powder B to solution A in S2-3 is (1-2):

10.

7. The composition containing mesoporous hydroxyapatite repair material according to claim 2, characterized in that: The amount of tea polyphenols added in S2-3 is 0.3 to 0.5 times the mass of powder B.

8. A method for preparing a composition containing a mesoporous hydroxyapatite repair material according to any one of claims 1 to 7, characterized in that: The specific steps of the preparation method are as follows: S8-1: Add sodium lauryl sulfate, potassium sorbate, stannous fluoride, and a moisturizer to deionized water at 30-40°C according to the formula ratio and stir for 10-20 minutes to obtain component A; S8-2: Add composite mesoporous hydroxyapatite and calcium phosphate to a dry powder mixer and mix at a speed of 100-200 r / min for 10-20 minutes. Then add hydrated silica, increase the speed to 200-300 r / min, and continue mixing for 5-10 minutes to obtain component B; S8-3: Add component B to component A, stir at a speed of 700-800 r / min for 30 minutes, add xanthan gum, and homogenize for 5-10 minutes to obtain the composition containing the mesoporous hydroxyapatite repair material.

9. The method for preparing a composition containing a mesoporous hydroxyapatite repair material according to claim 8, characterized in that: The stirring speed in S8-1 is 500-600 r / min.

10. The method for preparing a composition containing mesoporous hydroxyapatite repair material according to claim 8, characterized in that: The homogenization pressure in S8-3 is 20-30 MPa.

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