Photoinduced rediscoloring antibacterial dentin desensitizer as well as preparation method and application thereof

Abstract

The invention discloses a photochromic antibacterial dentin desensitizer as well as a preparation method and application thereof, and belongs to the technical field of biological medicines. The desensitizer comprises tungsten oxide sub-nanowires, in particular glycerol modified tungsten oxide sub-nanowires. The desensitizer further comprises a matrix monomer, a diluting monomer and a photo-initiation system. The desensitizer prepared by the invention solves the problems of coating integrity and uniformity of the desensitizer in clinical operation, has long-term stability, and can effectively enhance the dentin desensitization effect. Meanwhile, the desensitizer disclosed by the invention can effectively inhibit invasion of external bacteria and can be applied to the fields of tooth sensitivity, tooth aesthetic repair and the like.

Description

Technical Field

[0001] This invention relates to the field of biomedicine, and more specifically, to a photosensitive recolorable antibacterial dentin desensitizer, its preparation method, and its application. Background Technology

[0002] The key to controlling dentin hypersensitivity symptoms and reducing secondary oral diseases lies in quickly, effectively, and adequately sealing dentinal tubules. Existing dentin desensitizing agents primarily work by penetrating the exposed demineralized dentin surface to seal dentinal tubules, and by reducing dentin nerve sensitivity through glutaraldehyde in their composition, thereby reducing dentin hypersensitivity symptoms caused by exposed dentinal tubules. However, commercially available dentin desensitizing agents are generally in a transparent liquid state, making it difficult for dentists to visually assess the evenness and completeness of application during clinical application. Furthermore, existing dentin desensitizing agents lack antibacterial properties, and their abrasion resistance needs further improvement.

[0003] The invention patent, "A Rapidly Effective Visualized Tooth Desensitizing Agent and Its Preparation Method," uses stained selenium-containing bioactive glass as a staining agent to achieve staining of dental plaque, thereby enhancing the visualization effect of the tooth desensitizing agent in clinical applications. However, the aforementioned tooth desensitizing agent stains dental plaque, and the staining area does not completely correspond to the exposed dentin area. Furthermore, this staining lacks reversibility, making it difficult to apply to desensitizing and restoring tooth tissue located in the aesthetic zone. Summary of the Invention

[0004] To address the above problems, this invention provides a photosensitive recolorable antibacterial dentin desensitizing agent, its preparation method, and its application.

[0005] The desensitizing agent utilizes the photochromic effect of tungsten oxide subnanowires. Upon irradiation with clinical blue light, the agent turns blue, which helps determine the application area and homogeneity. Furthermore, the agent reverts to its initial color naturally within 48-72 hours to meet clinical aesthetic requirements. In an aqueous environment, the agent forms a stable interaction with dentin collagen through multi-level interactions based on their size characteristics, significantly enhancing the stability of the interaction between the desensitizing agent and dentin in a humid environment. Simultaneously, the agent exhibits excellent antibacterial properties, effectively resisting the invasion of oral pathogens.

[0006] To achieve the above objectives, the present invention adopts the following technical solution: This invention provides a photosensitive, recolorable, antibacterial dentin desensitizer, characterized in that the desensitizer comprises tungsten oxide subnanowires.

[0007] Preferably, the tungsten oxide subnanowires can be synthesized by screening tungsten-containing precursors, aliphatic alcohol selective ligands, and organic solvents. The tungsten-containing precursors include, but are not limited to, tungsten chloride, tungsten selenide, and tungsten isopropoxide; the aliphatic alcohol selective ligands include, but are not limited to, aliphatic alcohols with a hydrocarbon backbone of 6-22 carbon atoms, such as 9-octadecen-1-ol and 1-decyl alcohol; and the organic solvents include, but are not limited to, methanol, ethanol, n-propanol, acetone, and formamide.

[0008] More preferably, the tungsten oxide subnanowires are glycerol-modified tungsten oxide subnanowires. Specifically, the glycerol-modified tungsten oxide subnanowires are prepared by reacting tungsten chloride with 1-decyl alcohol and ethanol.

[0009] The most preferred method is to obtain the glycerol-modified tungsten oxide subnanowires by stirring tungsten chloride, 1-decyl alcohol, and ethanol in a reaction vessel, heating the mixture, cooling it to room temperature, washing the product with n-octane, adding glycerol, shaking and mixing thoroughly, and then allowing it to stand in an oven.

[0010] This invention provides a photosensitive, recolorable, antibacterial dentin desensitizing agent, characterized in that the desensitizing agent comprises glycerol-modified tungsten oxide subnanowires and a resin matrix. The resin matrix includes, but is not limited to, one or more of acrylamide resin monomers, carboxylic acid monomers, sulfonic acid monomers, quaternary ammonium salt monomers, and alcohol monomers. Specifically, the acrylamide resin monomers include, but are not limited to, one or more of acrylamide, methacrylamide, and N-isopropylacrylamide; the carboxylic acid monomers include, but are not limited to, one or more of acrylic acid, methacrylic acid, and maleic acid.

[0011] Preferably, the resin matrix is ​​hydroxyethyl methacrylate. The desensitizing agent also includes glutaraldehyde and water.

[0012] This invention provides a photosensitive, recolorable, antibacterial dentin desensitizing agent, characterized in that the desensitizing agent comprises glycerol-modified tungsten oxide subnanowires, matrix monomers, diluent monomers, and a photoinitiation system.

[0013] Preferably, the matrix monomer and diluent monomers in the desensitizing agent include, but are not limited to, one or more acrylate monomers such as triethylene glycol dimethacrylate, ethyl carbamate dimethacrylate, and bisphenol A ethoxylated dimethacrylate; the photoinitiating component includes, but is not limited to, one or more of camphorquinone, ethyl benzoate, and 2,4,6-trimethylbenzoyl-diphenylphosphine oxide. The desensitizing agent also includes an organic solvent component, including, but not limited to, one or more of ethanol, dimethyl sulfoxide, and acetone.

[0014] This invention provides a glycerol-modified tungsten oxide subnanowire, characterized in that the glycerol-modified tungsten oxide subnanowire is prepared by reacting tungsten chloride with 1-decyl alcohol and ethanol.

[0015] The most preferred method is to obtain the glycerol-modified tungsten oxide subnanowires by stirring tungsten chloride, 1-decyl alcohol, and ethanol in a reaction vessel, heating the mixture, cooling it to room temperature, washing the product with n-octane, adding glycerol, shaking and mixing thoroughly, and then allowing it to stand in an oven.

[0016] The present invention also provides a method for preparing the desensitizing agent formulation or the glycerol-modified tungsten oxide subnanowires.

[0017] The present invention also provides the use of tungsten oxide subnanowires in desensitizing agents. The desensitizing agent is used as an antibacterial dentin desensitizing agent, and the tungsten oxide subnanowires are preferably glycerol-modified tungsten oxide subnanowires.

[0018] The present invention also provides the application of the aforementioned desensitizing agent and tungsten oxide subnanowires in tooth sensitivity, dental aesthetic restoration, and related pharmaceuticals.

[0019] Beneficial effects The desensitizing agent provided by this invention: 1. The material itself has a stable structure and stable interaction with dentin, thus effectively enhancing the long-term stability of dentin desensitization; 2. It effectively inhibits the invasion of external bacteria; 3. Its photochromic properties ensure that medical personnel can fully coat and protect sensitive tooth tissues, while its photochromic properties ensure aesthetics. Attached Figure Description

[0020] Figure 1 Tungsten oxide subnanowires in ethanol solution.

[0021] Figure 2 Glycerol-modified tungsten oxide subnanowire solution.

[0022] Figure 3 Example 1: Light micrograph of the desensitizing agent.

[0023] Figure 4 Light micrographs of the desensitizing agent immediately after 20 seconds and 24 hours after irradiation with blue light in Example 2 (Left: immediate state after irradiation in Example 2; Right: light micrograph of Example 2 24 hours after irradiation).

[0024] Figure 5 Electron micrographs of the sealing effect of desensitizing agents on dentinal tubules: A: Artificially simulated worn dentin surface (dentinal tubules exposed); B: Dentin surface after treatment with commercial desensitizing agent Gluma; C: Dentin surface after treatment in Example 1 of this invention; D: Dentin surface after treatment in Example 2 of this invention.

[0025] Figure 6 Electron micrographs of sealing stability after toothbrush wear test: A: Dentin surface after treatment with commercial desensitizing agent Gluma (after simulating mechanical aging for 6 months); B: Dentin surface after treatment with non-light-cured desensitizing agent of Example 1 of the present invention (after simulating mechanical aging for 6 months); C: Dentin surface after treatment with non-light-cured desensitizing agent of Example 1 of the present invention (after simulating mechanical aging for 6 months).

[0026] Figure 7 Antibacterial effect of light-cured dentin desensitizer in Example 2 (Ctrl: blank control group; R: commercial resin group; RE: ethanol-modified commercial resin group; RW: solid desensitizer in Example 2). Detailed Implementation

[0027] The present invention will now be described in further detail with reference to specific embodiments. The given embodiments are merely illustrative of the invention and not intended to limit its scope. The embodiments provided below can serve as a guide for further improvements by those skilled in the art and do not constitute a limitation on the invention in any way.

[0028] Unless otherwise specified, the experimental methods used in the following examples are conventional methods, performed according to the techniques or conditions described in the literature in this field or according to the product instructions. Unless otherwise specified, the materials and reagents used in the following examples are commercially available.

[0029] Preparation of glycerol-modified tungsten oxide subnanowires of the present invention: 30 mg of tungsten hexachloride was dissolved in 5 mL of 1-decyl alcohol, 5 mL of anhydrous ethanol was added and stirred for 10 min, heated at 180 °C for 1 h in a reaction vessel, cooled to room temperature, the product was washed three times with 10 mL of n-octane, 5 mL of glycerol was added and thoroughly shaken and mixed, and the mixture was allowed to stand in a 60 °C oven for 24 h to obtain glycerol-modified tungsten oxide subnanowires.

[0030] The glycerol-modified tungsten oxide subnanowire solution of the present invention, such as Figure 2 As shown.

[0031] Preparation of the photosensitive, recolorable, antibacterial dentin desensitizing agent of the present invention: It includes two types: UV-curable and non-UV-curable. (1) Non-photocurable desensitizer: The liquid desensitizer was prepared by using 2-10 wt% glycerol-modified tungsten oxide sub-nanowires, 1-20 wt% hydroxyethyl methacrylate, 2-10 wt% glutaraldehyde, and 60%-95 wt% water.

[0032] (2) Light-cured dentin desensitizer, composed of 10%-70% bisphenol A-glycidyl methacrylate, 5%-50% hydroxyethyl methacrylate, 0.5%-10% glycerol-modified tungsten oxide sub-nanowires, 0.5%-5% camphorquinone and ethyl benzoate, and 0%-20% organic solvent.

[0033] Example 1: Non-photocurable desensitizing agent: Light micrograph of the desensitizing agent in Example 1 is shown below. Figure 3 As shown. Rinse the tooth structure thoroughly. Use a small brush to apply a small amount of desensitizing agent evenly to the surface of the sensitive tooth structure. Let it sit for 30 seconds to 2 minutes. Observe whether the area turning blue corresponds to the area of ​​the sensitive tooth structure. If it is not completely covered, continue the above steps.

[0034] Example 2: Light-cured dentin desensitizing agent: Light micrographs of the desensitizing agent immediately after 20 seconds and 24 hours after blue light irradiation in Example 2 are shown below. Figure 4 As shown, left side: immediate state after light exposure in Example 2; right side: light microscopy image 24 hours after light exposure in Example 2. Rinse the tooth tissue thoroughly, apply a small amount of desensitizing agent to the sensitive tooth tissue surface using a small brush, and expose to light for 10-20 seconds. Observe whether the area turning blue corresponds to the area of ​​the sensitive tooth tissue. If it is not completely covered, continue the above procedure.

[0035] Experiments were conducted using the photosensitive, recolorable, antibacterial dentin desensitizing agent of the present invention, and the results are as follows: Electron microscopy shows the sealing effect of the desensitizing agent of this invention on dentinal tubules. Figure 5 As shown. A represents an artificially simulated worn dentin surface (exposed dentinal tubules); B represents the dentin surface treated with the commercially available desensitizing agent Gluma; C represents the dentin surface treated in Example 1 of this invention; and D represents the dentin surface treated in Example 2 of this invention. From... Figure 5 As can be seen, the photosensitive recolorable antibacterial dentin desensitizer of the present invention has better coating uniformity and integrity than existing commercial desensitizers. It can quickly, effectively and fully seal dentinal tubules, thereby controlling dentin hypersensitivity symptoms and reducing secondary oral diseases.

[0036] Toothbrush abrasion test followed by closed-loop stability electron microscopy. Figure 6 As shown. Wherein, A: Dentin surface treated with the commercially available desensitizing agent Gluma (after simulating six months of mechanical aging); B: Dentin surface treated with the non-light-cured desensitizing agent of Example 1 of this invention (after simulating six months of mechanical aging); C: Dentin surface treated with the light-cured desensitizing agent of Example 2 of this invention (after simulating six months of mechanical aging). From Figure 6As can be seen, the photosensitive recolorable antibacterial dentin desensitizer of the present invention can form a stable interaction with dentin collagen in an aqueous environment, effectively sealing exposed dentinal tubules, exhibiting good stability, and can effectively enhance the dentin desensitization effect in the long term.

[0037] The antibacterial effect of the light-cured dentin desensitizer of the present invention is as follows: Figure 7 As shown. Wherein, Ctrl: blank control group; R: commercial resin group; RE: ethanol-modified commercial resin group; RW: solid desensitizing agent from Example 2. Figure 7 As can be seen, the photosensitive recolorable antibacterial dentin desensitizer of the present invention has excellent antibacterial effect, thereby effectively inhibiting or resisting the invasion of oral pathogenic microorganisms.

[0038] The present invention has been described in detail above. For those skilled in the art, the invention can be practiced in a wide range of ways with equivalent parameters, concentrations, and conditions without departing from its spirit and scope, and without requiring unnecessary experiments. Although specific embodiments have been given, it should be understood that further modifications can be made to the invention. In summary, according to the principles of the invention, this application is intended to include any changes, uses, or improvements to the invention, including changes made using conventional techniques known in the art that depart from the scope disclosed herein. Some of the essential features can be applied within the scope of the following appended claims.

Claims

1. A photochromic antibacterial dentin desensitizer, characterized in that, The desensitizer comprises tungsten oxide sub-nanowires.

2. The desensitizer of claim 1, wherein The tungsten oxide sub-nanowires are glycerol-modified tungsten oxide sub-nanowires. The glycerol-modified tungsten oxide sub-nanowires are prepared by mixing and reacting tungsten chloride with 1-decanol and ethanol.

3. The desensitizing agent as described in claim 2, characterized in that, The glycerol-modified tungsten oxide sub-nanowires are prepared by stirring tungsten chloride, 1-decanol and ethanol, heating in a reaction kettle, washing the product with n-octane after cooling to room temperature, adding glycerol, fully shaking and mixing, and standing in an oven.

4. A photochromic antibacterial dentin desensitizer, characterized in that, The desensitizer comprises glycerol-modified tungsten oxide sub-nanowires and a resin matrix. The resin matrix comprises one or more of acrylamide resin monomers, carboxylic acid monomers, sulfonic acid monomers, quaternary ammonium salt monomers and alcohol monomers. The acrylamide resin monomers comprise one or more of acrylamide, methacrylamide and N-isopropyl acrylamide; the carboxylic acid monomers comprise one or more of acrylic acid, methacrylic acid and maleic acid.

5. The desensitizing agent as described in claim 4, characterized in that, The resin matrix is hydroxyethyl methacrylate. The desensitizer further comprises glutaraldehyde and water.

6. A photo-reversible color-changing antibacterial dentin desensitizer, characterized in that, The desensitizer comprises glycerol-modified tungsten oxide sub-nanowires, matrix monomers, dilution monomers and a photoinitiating system.

7. The desensitizing agent as described in claim 6, characterized in that, The matrix monomers and dilution monomers in the desensitizer comprise, but are not limited to, triethylene glycol dimethacrylate, dimethylaminoethyl methacrylate, bisphenol A ethoxylated dimethyl acrylate and other acrylate monomers; the photoinitiating components comprise, but are not limited to, camphorquinone, ethyl benzoate, 2,4,6-trimethylbenzoyl-diphenyl phosphine oxide and the like. The desensitizer further comprises an organic solvent component, which comprises, but is not limited to, ethanol, dimethyl sulfoxide, acetone and the like.

8. A glycerol-modified tungsten sub-nanowire, characterized by, The glycerol-modified tungsten oxide sub-nanowires are prepared by mixing and reacting tungsten chloride with 1-decanol and ethanol. The glycerol-modified tungsten oxide sub-nanowires are prepared by stirring tungsten chloride, 1-decanol and ethanol, heating in a reaction kettle, washing the product with n-octane after cooling to room temperature, adding glycerol, fully shaking and mixing, and standing in an oven.

9. The desensitizer of any one of claims 1-7 or the preparation method of the glycerol-modified tungsten oxide sub-nanowires of claim 8.

10. Use of the desensitizer of any one of claims 1-7 or the tungsten oxide sub-nanowires in dental sensitivity, dental restoration and medicine.

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