Dental filling material of polyphenol modified magnesium-based powder / biphase calcium phosphate composite powder

Abstract

The invention discloses a tooth filling material based on polyphenol and collagen modified magnesium-based powder / biphase calcium phosphate composite powder, and a preparation method comprises the following steps: dissolving a polyphenol compound and magnesium-based powder / biphase calcium phosphate composite powder in absolute ethyl alcohol, adding an alkaline solution, adjusting the solution to be alkaline, and stirring uniformly; stirring to obtain polyphenol modified magnesium-based powder / biphase calcium phosphate composite powder; dissolving collagen and the centrifuged product into deionized water, and adjusting to a proper concentration; stirring to immerse the polyphenol modified magnesium-based powder / biphase calcium phosphate composite powder into the collagen solution; and adding ammonium persulfate to agglomerate the collagen to obtain the magnesium-based powder / biphase calcium phosphate composite powder based on polyphenol and collagen modification. According to the tooth filling filler as well as the preparation method and the application thereof, a new solution is provided for the field of dental implantation.

Description

Technical Field

[0001] The present invention belongs to the field of biomaterials, and in particular relates to a tooth filling material based on polyphenol and collagen modified magnesium-based powder / biphasic calcium phosphate composite powder, and a preparation method and application thereof. Background Art

[0002] Polyphenols are a class of compounds widely found in nature. Research has shown that they possess multiple bioactive properties, including anti-inflammatory, antioxidant, antibacterial, and angiogenic properties. Currently, numerous studies have investigated the incorporation of polyphenols into tissue repair materials to promote wound healing. Collagen is a material with extremely high biocompatibility and excellent mechanical properties. It is naturally degraded by the human body without causing rejection, and it remains relatively stable under external forces. Collagen also exhibits excellent properties in promoting cell growth and tissue repair, facilitating the repair and regeneration of wounds and surrounding tissues.

[0003] Biphasic calcium phosphate (BCP) is a bioceramic material composed of a mixture of hydroxyapatite (HA) and β-tricalcium phosphate (β-TCP) in a specific ratio. It exhibits excellent biocompatibility, bioactivity, degradation, osteoconductivity, and osteoinduction. These properties have led to its widespread application in dental implants, particularly in the osseointegration process between implants and alveolar bone.

[0004] The mechanical properties of magnesium-based powders are close to those of human bones, and the Mg released 2+ Magnesium is an essential element for life. As a dental filling material, magnesium-based powder exhibits excellent biodegradability and is gradually absorbed by the body over time, reducing the long-term complications associated with traditional metal fillings. Current methods for using magnesium-based powder as dental fillings suffer from issues such as a lack of tissue adhesion, slow bone regeneration, poor regulation of the oral microenvironment, and the inability to uniformly and effectively degrade over time.

[0005] Currently, there is no dental filling material based on polyphenol and collagen modified magnesium-based powder / biphasic calcium phosphate composite powder, which has good biocompatibility, mechanical properties and mineralization ability. Compared with other dental filling materials, the modification of polyphenols and collagen improves the tissue integration ability of the material and improves the physical properties of the material. At the same time, polyphenols can also synergize the hydrogen released by magnesium-based materials to play anti-inflammatory and antioxidant effects. The combination of magnesium-based powder and biphasic calcium phosphate can improve the mechanical properties of dental filling materials, such as tensile strength and toughness, which is crucial for stability and durability under chewing pressure. Biphasic calcium phosphate can also promote the remineralization of teeth and bones, and the degradation products also help tooth repair. Summary of the Invention

[0006] The present invention aims to provide a method for preparing and applying a dental filling material based on a polyphenol- and collagen-modified magnesium-based powder / biphasic calcium phosphate composite powder. By utilizing the antioxidant and anti-inflammatory properties of polyphenols, the magnesium-based powder / biphasic calcium phosphate composite powder is modified with polyphenols, which are then modified with collagen. This method yields a dental filling material based on the polyphenol- and collagen-modified magnesium-based powder / biphasic calcium phosphate composite powder with excellent biocompatibility and mineralization capacity. This preparation method not only enhances the filler's mechanical properties but also improves its bioactivity and biocompatibility, making it a highly effective dental restorative material.

[0007] The present invention provides a method for preparing a dental filling material based on polyphenol and collagen modified magnesium-based powder / biphasic calcium phosphate composite powder, comprising the following steps:

[0008] Step 1: dissolving a polyphenol compound and a magnesium-based powder / biphasic calcium phosphate composite powder in anhydrous ethanol, adding an alkaline solution to adjust the polyphenol solution to alkalinity, stirring to obtain a polyphenol-modified magnesium-based powder, and then centrifuging;

[0009] Step 2: adding collagen and the above centrifugal product into deionized water, adding ammonium persulfate and stirring to form a collagen-modified polyphenol-modified magnesium-based powder / biphasic calcium phosphate composite powder;

[0010] Step 3: The solution obtained in step 2 is frozen and dried, and then the dried powder is ground to reduce the particle size.

[0011] Furthermore, in step 1: magnesium-based powder includes but is not limited to magnesium, magnesium alloy, and magnesium hydride.

[0012] Furthermore, in step 1: polyphenols include but are not limited to dopamine, tannic acid, and gallic acid.

[0013] Furthermore, in step 1: the concentration of the magnesium-based powder in anhydrous ethanol is 0.001 to 1 g / ml; the concentration of the biphasic calcium phosphate in anhydrous ethanol is 0.001 to 1 g / ml; and the concentration of the alkaline solution is 0.01 to 1 g / ml.

[0014] Furthermore, in step 1: the temperature of anhydrous ethanol is 10-40° C., and the stirring time is 30 min-24 h.

[0015] Furthermore, in step 2: the mass of collagen is 0.01 to 2 g.

[0016] Furthermore, in step 2: the stirring time is 30 min to 6 h.

[0017] The tooth filling material based on polyphenol and collagen modified magnesium-based powder / biphasic calcium phosphate composite powder of the present invention is prepared according to the preparation method of first modifying the magnesium-based powder / biphasic calcium phosphate composite powder with polyphenol and then modifying it with collagen.

[0018] The invention discloses a tooth filling material based on polyphenol and collagen modified magnesium-based powder / biphasic calcium phosphate composite powder, which is used in the preparation of medical materials for tooth restoration.

[0019] The beneficial technical effects of the present invention compared with the prior art are:

[0020] 1. The present invention is based on a dental filling material of polyphenol and collagen modified magnesium-based powder / biphasic calcium phosphate composite powder. The combination of magnesium-based powder and biphasic calcium phosphate can improve the mechanical properties of the dental filling material, such as tensile strength and toughness, which are crucial for stability and durability under chewing pressure. Biphasic calcium phosphate can also promote the remineralization of teeth and bones. The Mg metabolized by both can improve the mechanical properties of the dental filling material, such as tensile strength and toughness. 2+ , Ca 2+ Both are ions needed for human metabolism and help repair teeth.

[0021] 2. The dental filling material of the present invention is based on polyphenol and collagen modified magnesium-based powder / biphasic calcium phosphate composite powder, which isolates the magnesium-based powder from the environment to a certain extent, reduces the corrosion rate of the magnesium-based powder, and at the same time, polyphenol can regulate the degradation rate and hydrogen release rate of the powder, thereby improving the corrosion resistance of the magnesium-based powder and the biocompatibility of the interface, and avoiding the rapid degradation of the magnesium-based powder.

[0022] 3. The polyphenols and collagen of the present invention can improve the tissue adhesion of the material, and can also improve the biocompatibility of the material and promote cell proliferation and differentiation, which is particularly important for tooth filling materials because it can promote the repair and regeneration of tooth tissue. The hydrogen released by the polyphenols and magnesium-based powder synergistically plays an anti-inflammatory and antioxidant role. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] Figure 1 This is an SEM image of the magnesium-based powder modified with polyphenols and collagen prepared in an example of the present invention.

[0024] Figure 2 This is a SEM image of the biphasic calcium phosphate modified with polyphenols and collagen prepared in an embodiment of the present invention.

[0025] Figure 3 This is an SEM image of the magnesium-based powder / biphasic calcium phosphate composite powder modified with polyphenols and collagen prepared in an embodiment of the present invention.

[0026] Figure 4This is a surface element distribution diagram of the magnesium-based powder / biphasic calcium phosphate composite powder modified with polyphenols and collagen prepared in an embodiment of the present invention.

[0027] Figure 5 This is the FTIR graph of the biphasic calcium phosphate modified with polyphenols and collagen prepared in an embodiment of the present invention.

[0028] Figure 6 This is the FTIR spectrum of the magnesium-based powder modified with polyphenols and collagen prepared in an example of the present invention. DETAILED DESCRIPTION

[0029] The present invention is further described in detail below with reference to the accompanying drawings and specific embodiments.

[0030] The present invention provides a method for preparing a dental filling material based on a magnesium-based powder / biphasic calcium phosphate composite powder modified with polyphenols and collagen, comprising the following steps:

[0031] Step 1: dissolving the polyphenol compound and magnesium-based powder / biphasic calcium phosphate composite powder in anhydrous ethanol, adding an alkaline solution, adjusting the polyphenol solution to alkaline, stirring to obtain polyphenol-modified magnesium-based powder / biphasic calcium phosphate composite powder, and then centrifuging.

[0032] Furthermore, magnesium-based powders include but are not limited to magnesium, magnesium alloys, and magnesium hydride.

[0033] Furthermore, polyphenols include but are not limited to dopamine, tannic acid, and gallic acid.

[0034] Furthermore, the concentration of the magnesium-based powder in anhydrous ethanol is 0.001 to 1 g / ml; the concentration of the biphasic calcium phosphate in anhydrous ethanol is 0.001 to 1 g / ml; and the concentration of the alkaline solution is 0.01 to 1 g / ml.

[0035] Furthermore, the temperature of the anhydrous ethanol is 10-40° C., and the stirring time is 30 min-24 h.

[0036] Step 2: Add collagen and the above centrifugal product into deionized water, add ammonium persulfate and stir to make collagen-modified polyphenol-modified magnesium-based powder / biphasic calcium phosphate composite powder.

[0037] Furthermore, the mass of collagen is 0.01 to 2 g.

[0038] Furthermore, the stirring time is 30 minutes to 6 hours.

[0039] Step 3: The solution obtained in step 2 is frozen and dried, and then the dried powder is ground to reduce the particle size.

[0040] The tooth filling material of the present invention is based on polyphenol and collagen modified magnesium-based powder / biphasic calcium phosphate composite powder, which is prepared according to the preparation method of the polyphenol modified magnesium-based powder / biphasic calcium phosphate composite powder and then modified with collagen.

[0041] The invention discloses a tooth filling material based on polyphenol and collagen modified magnesium-based powder / biphasic calcium phosphate composite powder, which is used in the preparation of medical materials for tooth restoration.

[0042] Example 1:

[0043] Step 1: Add 0.02 g of dopamine to 6 ml of anhydrous ethanol, then add 0.1 g of magnesium and 0.1 g of biphasic calcium phosphate, add 0.2 ml of NaOH solution (concentration of 0.5 g / ml) and stir for 10 minutes to obtain a prepolymer solution.

[0044] Step 2: Add 1 g of collagen to the prepolymer solution obtained in step 1, and continue stirring for 2 hours to obtain a solution of a tooth filling material containing polyphenol-modified magnesium-based powder / biphasic calcium phosphate and composite collagen.

[0045] Step 3: The solution obtained in step 2 is frozen and dried, and then the dried powder is ground to reduce the particle size.

[0046] Example 2:

[0047] Step 1: Add 0.02 g of dopamine to 6 ml of anhydrous ethanol, then add 0.1 g of magnesium-zinc alloy and 0.1 g of biphasic calcium phosphate, add 0.2 ml of NaOH solution (concentration of 0.5 g / ml) and stir for 10 minutes to obtain a prepolymer solution.

[0048] Step 2: Add 1 g of collagen to the prepolymer solution obtained in step 1, and continue stirring for 2 hours to obtain a solution of a tooth filling material containing polyphenol-modified magnesium-zinc alloy / biphasic calcium phosphate and composite collagen.

[0049] Step 3: The solution obtained in step 2 is frozen and dried, and then the dried powder is ground to reduce the particle size.

[0050] Example 3:

[0051] Step 1: Add 0.02 g of dopamine to 6 ml of anhydrous ethanol, then add 0.1 g of magnesium hydride and 0.1 g of biphasic calcium phosphate, add 0.2 ml of NaOH solution (concentration of 0.5 g / ml) and stir for 10 minutes to obtain a prepolymer solution.

[0052] Step 2: Add 1 g of collagen to the prepolymer solution obtained in step 1, and continue stirring for 2 hours to obtain a solution of a tooth filling material containing polyphenol-modified magnesium hydride / biphasic calcium phosphate and composite collagen.

[0053] Step 3: The solution obtained in step 2 is frozen and dried, and then the dried powder is ground to reduce the particle size.

[0054] Figure 1 This is an SEM image of the magnesium-based powder modified with polyphenols and collagen prepared in an example of the present invention. Figure 1 (a) The surface of the unmodified magnesium-zinc alloy is smoother and the particle size is smaller. After polyphenol modification, Figure 1 (b) The surface becomes rough, the particle size increases significantly and some small holes appear. After collagen modification Figure 1 (c) The surface has almost no pores and no obvious particles. The particle size is significantly increased, which may be caused by the aggregation of collagen, proving the successful modification of the magnesium-zinc alloy by polyphenols and collagen.

[0055] Figure 2 This is a SEM image of the biphasic calcium phosphate modified with polyphenols and collagen prepared in an embodiment of the present invention. Figure 2 (a) is unmodified biphasic calcium phosphate, after polyphenol modification Figure 2 (b) There are obvious particles attached to the surface, and then after being wrapped by collagen Figure 2 (c), the surface was almost completely coated, indicating the successful modification of biphasic calcium phosphate by polyphenols and collagen.

[0056] Figure 3 This is an SEM image of a magnesium-based powder / biphasic calcium phosphate composite powder modified with polyphenols and collagen prepared in an embodiment of the present invention. Figure 3 (a) is the overall picture, Figure 3 (b) and (c) are parts of the whole picture. Figure 3 The bulk object in (b) is a magnesium-zinc alloy modified with polyphenols and collagen. Figure 3 The object in (c) is a homogeneous mixture of polyphenol- and collagen-modified biphasic calcium phosphate.

[0057] Figure 4 This is a surface element distribution diagram of the magnesium-based powder / biphasic calcium phosphate composite powder modified with polyphenols and collagen prepared in an embodiment of the present invention. Figure 4 (a) is the selected area image, Figure 4 (b)(c)(d)(e) are the distribution diagrams of Ca, P, Mg and Zn in the selected area, respectively. Ca and P are the characteristic elements of duplex calcium phosphate, and Mg and Zn are the characteristic elements of magnesium-zinc alloy. This further illustrates that magnesium-zinc alloy and duplex calcium phosphate exist in the selected area and are evenly distributed.

[0058] Figure 5This is the FTIR spectrum of biphasic calcium phosphate modified with polyphenols and collagen prepared in accordance with the present invention. The curves in the figure, from bottom to top, are: biphasic calcium phosphate (BCP), dopamine-modified biphasic calcium phosphate (PDA-BCP), and collagen-modified dopamine-modified biphasic calcium phosphate (COL-PDA-BCP). The 1000-500 cm -1 The peak is the fingerprint region. The peak here is related to biphasic calcium phosphate and is at 1550cm -1 The peaks are NH bending and 3500-3200 cm -1 The peaks of NH and OH stretching vibrations further prove the successful modification of polyphenols, 1650cm -1 The peak is the stretching of C=O, and the decrease in the intensity of the peak of polyphenol-modified biphasic calcium phosphate further proves the successful modification of collagen.

[0059] Figure 6 This is the FTIR spectrum of the magnesium-based powder modified with polyphenols and collagen prepared in the present invention. The curves from bottom to top are: magnesium-zinc alloy (MZ), dopamine-modified magnesium-zinc alloy (PDA-MZ), and collagen-modified dopamine-modified magnesium-zinc alloy (COL-PDA-MZ). 1000-500 cm -1 The peak is the fingerprint region. The peak here is related to magnesium-zinc alloy and is at 1550cm -1 The peaks are NH bending and 3500-3200 cm -1 The peaks of NH and OH stretching vibrations further prove the successful modification of polyphenols, 1650cm -1 The peak is the stretching of C=O, and the decrease in the intensity of the peak compared to the polyphenol-modified magnesium-zinc alloy further proves the successful modification of collagen.

[0060] The present invention provides a method for preparing a dental filling material based on a polyphenol- and collagen-modified magnesium-zinc alloy / biphasic calcium phosphate composite powder, wherein the polyphenol- and collagen-modified magnesium-zinc alloy / biphasic calcium phosphate composite powder is prepared by the method described above; the dental filling material based on the polyphenol- and collagen-modified magnesium-zinc alloy / biphasic calcium phosphate composite powder can be widely used in the preparation of medical materials for dental restoration. Compared with other dental filling materials, the combination of polyphenols and collagen can promote the biomimetic remineralization of dentin, enhance the material's tissue integration ability, and improve the material's physical properties. At the same time, polyphenols can also synergize with the hydrogen released by the magnesium-based material to exert anti-inflammatory and antioxidant effects, and the degradation products can also contribute to tooth restoration.

Claims

1. A method for preparing a dental filling material based on polyphenol and collagen modified magnesium-based powder / biphasic calcium phosphate composite powder, characterized in that: The following steps are involved: Step 1: dissolving a polyphenol compound and a magnesium-based powder / biphasic calcium phosphate composite powder in anhydrous ethanol, adding an alkaline solution to adjust the polyphenol solution to alkalinity, stirring to obtain a polyphenol-modified magnesium-based powder, and then centrifuging; Step 2: adding collagen and the above centrifugal product into deionized water, adding ammonium persulfate and stirring to form a collagen-modified polyphenol-modified magnesium-based powder / biphasic calcium phosphate composite powder; Step 3: The solution obtained in step 2 is frozen and dried, and then the dried powder is ground to reduce the particle size.

2. The method for preparing a dental filling material based on polyphenol and collagen modified magnesium-based powder / biphasic calcium phosphate composite powder according to claim 1, characterized in that: In step 1: magnesium-based powder includes but is not limited to magnesium, magnesium alloy, and magnesium hydride.

3. The method for preparing a dental filling material based on polyphenol and collagen modified magnesium-based powder / biphasic calcium phosphate composite powder according to claim 1, characterized in that: In the step 1: polyphenols include but are not limited to dopamine, tannic acid, and gallic acid.

4. The method for preparing a dental filling material based on polyphenol and collagen modified magnesium-based powder / biphasic calcium phosphate composite powder according to claim 2, characterized in that: In the step 1, the concentration of the magnesium-based powder in anhydrous ethanol is 0.001 to 1 g / ml; the concentration of the biphasic calcium phosphate in anhydrous ethanol is 0.001 to 1 g / ml; and the concentration of the alkaline solution is 0.01 to 1 g / ml.

5. The method for preparing a dental filling material based on polyphenol and collagen modified magnesium-based powder / biphasic calcium phosphate composite powder according to claim 2, characterized in that: In the step 1, the temperature of the anhydrous ethanol is 10-40° C., and the stirring time is 30 min-24 h.

6. The method for preparing a dental filling material based on polyphenol and collagen modified magnesium-based powder / biphasic calcium phosphate composite powder according to claim 1, characterized in that: In the step 2: the mass of the collagen is 0.01 to 2 g.

7. The method for preparing a dental filling material based on polyphenol and collagen modified magnesium-based powder / biphasic calcium phosphate composite powder according to claim 5, characterized in that: In the step 2, the stirring time is 30 min to 6 h.

8. A tooth filling material based on polyphenol and collagen modified magnesium-based powder / biphasic calcium phosphate composite powder, characterized in that: The tooth filling filler is prepared according to the preparation method of polyphenol-modified magnesium-based powder biphasic calcium phosphate composited with collagen according to any one of claims 1 to 7.

9. A dental filling material based on polyphenol and collagen modified magnesium-based powder / biphasic calcium phosphate composite powder according to claim 8, characterized in that: Used in the preparation of medical materials for dental restoration.

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