Enamel-imitated composite crown repair material as well as preparation method and application thereof

Abstract

The invention discloses an enamel-imitated composite crown repairing material and a preparation method and application thereof, and relates to the field of ceramic oral cavity repairing, the repairing material comprises a composite matrix, a net-shaped wrapping structure and arginine, the net-shaped wrapping structure wraps the outer side of the composite matrix, and the arginine is grafted to the net-shaped wrapping structure; the composite matrix comprises a TZP bracket and polyaryletherketone. According to the invention, the composite matrix matched with the enamel in mechanical property is provided, and arginine is successfully and stably grafted on the outer side of the composite matrix by virtue of a net-shaped wrapping structure, so that the purposes of stably grafting arginine on a special interface of an organic-inorganic composite material and realizing special target surface modification of the organic-inorganic material are achieved.

Description

Technical Field

[0001] The present invention relates to the field of ceramic oral restoration, and in particular to an imitation enamel composite crown restoration material, a preparation method and an application thereof. Background Art

[0002] In the oral field, the incidence of food impaction is high and it is a common complication after restoration and reconstruction. The hardness of the occlusal surface of human enamel is about 4.6-5.5GPa, the elastic modulus is about 94GPa, and the interproximal surface hardness is about 4.0-4.7GPa, and the elastic modulus is about 80GPa. However, the hardness of existing commonly used restoration and reconstruction materials, such as single-layer zirconia, reaches 11.7-13.7GPa and the elastic modulus reaches 200GPa, which is much greater than that of enamel. There is a clear trend of mismatch in mechanical properties between restoration and reconstruction materials and enamel. When the oral cavity performs chewing function, in addition to the periodic cyclic contact of the occlusal surface, due to the physiological mobility of natural teeth, micro-contact will also occur between adjacent teeth, and the occlusal force will be transmitted through the adjacent parts. Due to the mismatch in mechanical properties between natural teeth and restorative materials, the greater the difference, the greater the micro-wear generated between the mating interface, resulting in loss of adjacent joints and the susceptibility to food impaction.

[0003] The adjacent areas are not in close contact, and there is a tiny gap of 3-21μm between them. The enamel in this area is exposed to the bacterial environment of the oral cavity, forming a biofilm. Due to the hidden nature of the adjacent areas, it is difficult to remove the biofilm in this area. The biofilm itself has a lubricating effect, but the bacteria in the dental plaque biofilm metabolize and produce acid, which leads to demineralization of hard tissue, rough surface, and even caries, which will aggravate the micro-wear of the adjacent areas and further aggravate food impaction.

[0004] Ceramic materials are widely used in dental restorations due to their excellent aesthetic properties, durability, and biocompatibility. However, their clinical applications are still limited by their fracture sensitivity and excessive wear on teeth. The polyaryletherketone family of specialty engineering plastics has become a hot topic in the international field of stomatology in recent years due to its chemical stability, wear resistance, thermoplasticity, biocompatibility, aesthetic advantages, and radiotransparency. Polyaryletherketone (PAEK) has good thermal stability, excellent mechanical properties, and biocompatibility, and has broader application prospects in the field of dental materials. However, the elastic modulus of pure PEAK is only about 5GPa, and its mechanical properties are insufficient, which limits its clinical application.

[0005] At present, conventional crown restoration materials still have the defects of low biomechanical matching with tooth enamel and poor micro-motion anti-wear effect.

[0006] Tooth enamel possesses two unique microstructural features: 1. Nanoscale hydroxyapatite (HA) crystals form a controlled nucleation and regular growth to form a micron-scale three-dimensional structure; 2. Organic components fill the gaps left by the inorganic components, combining to form a regularly arranged macrostructure. This naturally occurring, multi-level structure endows natural enamel with a unique fracture toughening mechanism. The ingenious structure of natural tooth enamel, as described above, offers inspiration for biomimetic design of restorative materials. The inorganic component provides a rigid scaffold, while the organic filling imparts the toughness and ductility of bone. The combination of inorganic and organic materials in this biomimetic structure imparts high yield strength and fracture toughness to the material, offering great potential for alternative treatment of edentulous or lost teeth.

[0007] Arginine (Arg), an amino acid present in human saliva, plays a crucial role in regulating the acid-base balance of dental plaque and the microecological balance. Alkali-producing bacteria in the oral cavity can rapidly metabolize free arginine in the biofilm into ammonia using the arginine deiminase system, thereby buffering acidic products and regulating the biofilm pH, protecting acid-sensitive bacterial communities within the biofilm and maintaining a non-cariogenic state within the biofilm. Exogenous arginine can be taken up and metabolized by bacteria within the biofilm, improving the cariogenic state of the biofilm. Furthermore, long-term exogenous arginine intake can stabilize the pH of the microecological environment, reduce the activity of cariogenic bacteria, minimize the formation of cariogenic biofilms, and regulate the surface microenvironment of dental crowns.

[0008] There is a bottleneck in interface functionalization in arginine grafting: arginine cannot be grafted stably, physical adsorption is easy to fall off, and long-term protection cannot be achieved. Stable arginine grafting can only be obtained through covalent bonding. Arginine needs to be covalently bonded with amino or carboxyl groups through condensation reactions, but the organic-inorganic matrix material lacks active groups, and the organic-inorganic special interface of the composite material needs to be further modified.

[0009] In view of this, this application is filed. Summary of the Invention

[0010] The purpose of the present invention is to provide an enamel-like composite crown restoration material, its preparation method and application. By providing a composite matrix that matches the mechanical properties of enamel, arginine is successfully and stably grafted onto the outside of the composite matrix with the help of a mesh wrapping structure, thereby solving the problem of arginine being unable to be stably grafted in the prior art.

[0011] First, an embodiment of the present invention provides an enamel-like composite crown restoration material, comprising a composite matrix, a reticular wrapping structure, and arginine, wherein the reticular wrapping structure is coated on the outside of the composite matrix, and the arginine is grafted onto the reticular wrapping structure; The composite matrix includes a TZP support and polyaryletherketone.

[0012] As an optional implementation manner, the TZP scaffold and the polyaryletherketone are arranged in alternating layers, and the mass ratio of the TZP scaffold to the polyaryletherketone in the composite matrix is ​​2.9-5.7:1.

[0013] As an optional embodiment, the network wrapping structure is formed by covalently bonding one side of the siloxane hydrolyzed by γ-aminopropyltriethoxysilane to the hydroxyl group on the surface of the composite matrix, and the amino group on the other side of the network wrapping structure can undergo a condensation reaction with the carboxyl group of arginine to complete grafting and coating.

[0014] As an optional embodiment, the hydroxyl groups on the surface of the composite matrix include hydroxyl groups on the TZP support and hydroxyl groups on the surface of the polyaryletherketone; The hydroxyl groups on the TZP scaffold are formed by functionalizing the TZP scaffold with H2O2; The hydroxyl groups on the surface of the polyaryletherketone are formed by irradiating the polyaryletherketone with UV light.

[0015] Secondly, the embodiment of the present invention also provides a method for preparing an imitation enamel composite crown restoration material, comprising the following steps: S1: freeze-casting nano-zirconia particles and sintering them to obtain a TZP scaffold to simulate the rigidity of the inorganic phase of enamel; the TZP particles account for 50-60 wt% of the freeze-cast slurry used; S2: Add TZP scaffold, generate polyaryletherketone (PEAK) by using Friedel-Crafts reaction principle, realize in situ polymerization of polyaryletherketone (PEAK), obtain TZP / PEAK composite matrix, and make the composite modulus approach the elastic modulus of enamel; S3: immersing the TZP / PEAK composite substrate in a hydrogen peroxide solution, stirring, taking it out, and sequentially washing and drying it; then irradiating it with UV light to modify the surface of the TZP / PEAK composite substrate with hydroxyl groups, i.e., performing a double-step hydroxylation modification; S4: placing the hydroxyl-modified TZP / PEAK composite matrix in a mixed solution of γ-aminopropyltriethoxysilane and anhydrous ethanol for reaction, washing with anhydrous ethanol and drying after the reaction to obtain a composite material grafted with APTES, i.e., APTES is covalently bonded to the interface through siloxane bonds; S5: Arginine, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide, and 1-hydroxybenzotriazole are weighed and added sequentially to a mixed solution of diisopropylethylamine and dimethylformamide to obtain a mixed solution containing arginine. The APTES-grafted composite material is immersed in the mixed solution containing arginine to react. After the reaction, the composite material is washed and dried to obtain an AMEM composite material. Specifically, in the presence of the activating agents EDC / HOBT, arginine is covalently grafted onto the exposed amino groups of APTES via an amide bond to obtain the arginine-based microecologically regulated enamel-mimicking composite material (AMEM).

[0016] As an optional implementation method, the Friedel-Crafts reaction principle described in S2 is used to generate polyaryletherketone, including using terephthaloyl chloride, isophthaloyl chloride and diphenyl ether as raw materials, aluminum oxide as a catalyst, and 1,2-dichloroethane as a solvent for polymerization reaction.

[0017] As an optional implementation, the concentration of the hydrogen peroxide solution in S3 is 15-25%, the stirring temperature is 50-60° C., the stirring time is 4-8 hours, and the UV irradiation time is 0.8-1.2 hours.

[0018] As an optional implementation method, the volume ratio of γ-aminopropyltriethoxysilane to anhydrous ethanol in S4 is 1:8-12, the reaction temperature is 70-90° C., and the reaction time is 10-14 hours.

[0019] As an alternative embodiment, the arginine concentration in the mixed solution containing arginine in S5 is 70-90 mg / ml, the reaction time is 20-30 hours, and the washing step includes washing at least twice with anhydrous DMF and at least three times with deionized water. It should be noted that the arginine grafting concentration is not limited, but is preferably 80 mg / ml.

[0020] Finally, an embodiment of the present invention further provides an application of an enamel-like composite crown restoration material, including using the material to prepare a dental restoration, wherein the dental restoration includes at least one of a fixed / implanted crown, a dental bridge, and a dental veneer.

[0021] Compared with the prior art, the embodiments of the present invention have the following advantages and beneficial effects: 1. The embodiment of the present invention provides a composite matrix that matches the mechanical properties of tooth enamel, and successfully stably grafts arginine onto the outside of the composite matrix with the help of a reticular wrapping structure, thereby achieving the purpose of stably grafting arginine at the special interface of the organic-inorganic composite material and realizing the special target surface modification of the organic-inorganic material.

[0022] 2. The synthetic enamel-like crown restoration material in the embodiments of the present invention exhibits an elastic modulus and hardness that matches that of tooth enamel, and at the same time has excellent strength and elastic-plastic properties, reducing enamel micro-wear caused by mechanical mismatch. Compared with commonly used materials, it has no significant effect on cytotoxicity in in vitro tests and has good biocompatibility in in vivo studies.

[0023] 3. The embodiment of the present invention adopts a "two-step hydroxylation (H2O2 oxidation of TZP + UV activation of PAEK) → silane coupling bridging (APTES) → arginine covalent grafting" process to stably graft arginine at the special interface of the organic-inorganic composite material, achieving a specific target surface modification of the organic-inorganic material. The grafted arginine is metabolized by oral bacteria to produce ammonia, which regulates the pH of the biofilm to a non-cariogenic state, reduces the formation of cariogenic biofilm, inhibits the activity of cariogenic bacteria, regulates the surface microenvironment of the crown, and prevents enamel demineralization and roughening. The lubrication of the healthy biofilm and the anti-friction properties of the matrix synergistically protect the adjacent enamel.

[0024] 4. The bionic crown restoration material prepared in the embodiment of the present invention, which is adapted to the bio-mechanical properties of enamel, can simultaneously achieve the matching of the biological and mechanical properties of enamel, and finally achieve the anti-micro-wear effect, which is beneficial to reduce the loss of adjacent joints and prevent the occurrence of food impaction. The micro-wear of adjacent enamel and the interaction of biofilm on adjacent micro-wear are analyzed, and further work is carried out from the perspectives of material anti-caries empowerment, reducing micro-wear of adjacent interface enamel, regulating the non-caries-causing metabolic state of adjacent biofilm, and exerting the synergistic wear-reducing effect of the two, so as to further achieve the long-term preservation of adjacent tooth tissues synchronized with the aging changes of natural teeth, and finally propose biotribological design principles and measures to enhance the long-term stability of tooth adjacent joints and prevent and treat food impaction, and provide a cognitive basis for the research and development of new adjacent restoration materials. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] In order to more clearly illustrate the technical solutions of the exemplary embodiments of the present invention, the following briefly introduces the drawings required for use in the examples. It should be understood that the following drawings only illustrate certain embodiments of the present invention and should not be considered as limiting the scope. A person of ordinary skill in the art can also derive other relevant drawings based on these drawings without inventive effort. In the drawings: Figure 1 This is the SEM image of the AMEM composite material prepared in Example 1; in Figure 1 b is Figure 1 A partial enlarged view of a; Figure 2 This is the surface element distribution diagram of the AMEM composite material prepared in Example 1; in Figure 2a corresponds to the Zr element, Figure 2 b corresponds to the O element, Figure 2 c corresponds to the C element, Figure 2 d corresponds to the N element, Figure 2 e is Figure 2 a. Figure 2 b. Figure 2 c and Figure 2 Composite image of d; Figure 3 This is the energy spectrum of the AMEM composite material prepared in Example 1; Figure 4 is 10 4 Surface morphology of interproximal enamel after tangential micro-wear in a chewing cycle; Figure 5 10 in Example 1 4 Surface morphology of AMEM after tangential fretting wear in a chewing cycle; Figure 6 is 10 4 Surface morphology of zirconia after tangential fretting wear in a chewing cycle; Figure 7 is 10 4 Surface morphology of glass ceramics after tangential fretting wear in a chewing cycle; Figure 8 is 10 4 PEAK surface morphology after tangential fretting wear in a chewing cycle; Figure 9 This is an electron microscope photograph of HGFs and the AMEM composite material prepared in Example 2 after co-culture for 24 hours. Figure 9 b is Figure 9 A partial enlarged view of a; Figure 10 This is an electron microscope photograph of HGFs and the AMEM composite material prepared in Example 3 after co-culture for 24 hours. Figure 10 b is Figure 10 A partial enlarged view of a; Figure 11 This is an electron microscope photograph of HGFs and the AMEM composite material prepared in Example 4 after co-culture for 24 hours. Figure 11 b is Figure 11 A partial enlarged view of a; Figure 12 This is an electron microscope photograph of HGFs and the AMEM composite material prepared in Example 1 after co-culture for 24 hours. Figure 12 b is Figure 12 A partial enlarged view of a; Figure 13 This is an electron microscope photograph of HGFs and the AMEM composite material prepared in Example 5 after co-culture for 24 hours. Figure 13 b is Figure 13A partial enlarged view of a; Figure 14 This is an electron microscope photograph of HGFs and the AMEM composite material prepared in Example 6 after co-culture for 24 hours. Figure 14 b is Figure 14 A partial enlarged view of a; Figure 15 15b is an electron microscopic photograph of HGFs and the TZP scaffold prepared in Example 1 after co-culture for 24 hours. Figure 15 A partial enlarged view of a; Figure 16 16b is an electron microscope photo of the composite crown repair material prepared in Comparative Example 1 after co-culture for 24 hours with HGFs. Figure 16 A partial enlarged view of a; Figure 17 is an electron microscope photo of HGFs co-cultured with ZrO2 for 24 hours, 17b is Figure 17 A partial enlarged view of a; Figure 18 is an electron microscopic photograph of HGFs and PEAK after co-culture for 24 hours, 18b is Figure 18 A partial enlarged view of a; Figure 19 19b is an electron microscope photograph of Streptococcus mutans co-cultured with the AMEM composite material prepared in Example 2 for 24 hours, and 19c is Figure 19 A partial enlarged view of a; Figure 20 20b is an electron microscope photograph of Streptococcus mutans co-cultured with the AMEM composite material prepared in Example 3 for 24 hours, and 20c is Figure 20 A partial enlarged view of a; Figure 21 21b is an electron microscope photograph of Streptococcus mutans co-cultured with the AMEM composite material prepared in Example 4 for 24 hours, and 21c is Figure 21 A partial enlarged view of a; Figure 22 22b is an electron microscope photograph of Streptococcus mutans co-cultured with the AMEM composite material prepared in Example 1 for 24 hours, Figure 22 A partial enlarged view of a; Figure 23 23b is an electron microscope photograph of Streptococcus mutans co-cultured with the AMEM composite material prepared in Example 5 for 24 hours, Figure 23 A partial enlarged view of a; Figure 24 24b is an electron microscope photograph of Streptococcus mutans co-cultured with the AMEM composite material prepared in Example 6 for 24 hours, and 24c is Figure 24 A partial enlarged view of a; Figure 2525b is an electron microscope photo of Streptococcus mutans co-cultured with the TZP scaffold prepared in Example 1 for 24 hours, and 25c is Figure 25 A partial enlarged view of a; Figure 26 26b is an electron microscope photo of Streptococcus mutans co-cultured with the composite crown repair material prepared in Comparative Example 1 for 24 hours, and 26c is Figure 26 A partial enlarged view of a; Figure 27 is an electron microscope photo of Streptococcus mutans co-cultured with ZrO2 for 24 hours, 27b is Figure 27 A partial enlarged view of a; Figure 28 is an electron microscope photo of Streptococcus mutans co-cultured with PEAK for 24 hours, 28b is Figure 28 A partial enlarged view of a; Figure 29 29b is an electron microscope photo of HGFs and the composite crown repair material prepared in Comparative Example 2 after co-culture for 24 hours. Figure 29 A partial enlarged view of a; Figure 30 30b is an electron microscope photo of HGFs and the composite crown repair material prepared in comparative example 3 after co-culture for 24 hours. Figure 30 A partial enlarged view of a; Figure 31 31b is an electron microscope photo of Streptococcus mutans co-cultured with the composite crown restoration material prepared in Comparative Example 2 for 24 hours. Figure 31 A partial enlarged view of a; Figure 32 32b is an electron microscope photo of Streptococcus mutans and the composite crown restoration material prepared in Comparative Example 3 after co-culture for 24 hours. Figure 32 A partial enlarged view of a. DETAILED DESCRIPTION

[0026] In order to make the purpose, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments.

[0027] Therefore, the detailed description of the embodiments of the present invention provided below is not intended to limit the scope of the claimed invention, but rather merely represents selected embodiments of the present invention. All other embodiments derived by persons of ordinary skill in the art based on the embodiments of the present invention without creative effort are intended to fall within the scope of protection of the present invention.

[0028] The present invention provides a method for preparing an enamel-like composite crown restoration material, comprising the following steps: S1: freeze-casting nano-zirconia particles (water is used as the solvent in the freeze-casting slurry, and the nano-zirconia content is in the range of 50-60wt%) and sintering to obtain a TZP scaffold with sufficient strength; S2: Add the TZP scaffold dried in step S1 to a 2L dry glass reactor equipped with mechanical stirring and nitrogen flow. Then, using the Friedel-Crafts reaction principle, terephthaloyl chloride, isophthaloyl chloride, and diphenyl ether as raw materials, aluminum oxide as a catalyst, and 1,2-dichloroethane as a solvent, generate PEAK at room temperature, atmospheric pressure, and a nitrogen atmosphere. PEAK is polymerized in situ to obtain a TZP / PEAK composite matrix. The mass ratio of TZP scaffold to poly(aryletherketone) in the TZP / PEAK composite matrix is ​​2.9-5.7:1. S3: Immerse the TZP / PEAK composite substrate in a 15-25% hydrogen peroxide solution at 50-60°C and stir for 4-8 hours, then take it out, rinse it with RO water, and dry it in an oven at 50-70°C; irradiate it with an ultraviolet high-pressure mercury lamp for 0.8-1.2 hours to modify the surface of the TZP / PEAK composite substrate with hydroxyl groups; S4: placing the hydroxyl-modified composite material in a mixed solution of APTES / anhydrous ethanol (volume ratio 1:8-12) at 70-90°C for 10-14 hours, and washing with anhydrous ethanol and drying after the reaction. S5: Arg, EDC and HOBT were weighed and added to a DIPEA / DMF (volume ratio 1: 20~30) mixed solution in sequence to obtain a mixed solution with an Arg concentration of 70~90 mg / ml. The APTES-grafted composite material was immersed in the mixed solution and placed under gentle stirring for 20~30 hours. After the reaction was completed, it was washed with anhydrous DMF at least twice, washed with RO water at least three times, and dried to obtain an arginine-modified composite material, namely, AMEM composite material.

[0029] In the crown restoration material of the embodiment of the present invention, TZP is functionalized with H2O2 to introduce a large number of hydroxyl groups that can serve as reaction sites. In addition, the carbonyl groups on the surface of PEAK are converted into hydroxyl groups through UV illumination. Furthermore, one side of the siloxane hydrolyzed with γ-aminopropyltriethoxysilane (APTES) is covalently bonded to the hydroxyl groups on the surface of the composite material to form a network-like wrapping. The grafting and coating are completed through a condensation reaction between the amino group at the other end and the carboxyl group of arginine, thereby achieving the stable grafting of arginine to the surface of the TZP / PEAK composite material.

[0030] The crown restoration material of this embodiment is designed to achieve mechanical properties that match those of tooth enamel, resulting in excellent biocompatibility and antibacterial properties. This synergistic mechanical-biological matching enhances compatibility between the restoration material and tooth enamel, thereby resisting fretting wear. This process is further subdivided into: preparing a biomimetic ceramic scaffold and toughening it with PEAK through in-situ polymerization. Furthermore, arginine is simultaneously modified and grafted onto the ceramic scaffold-PEAK material interface to regulate the biofilm microenvironment on the composite material surface.

[0031] In order to better demonstrate the significant effects of the embodiments of the present invention, specific embodiments and comparative examples will be designed below for verification.

[0032] Example 1: This embodiment of the present invention provides a method for preparing an enamel-like composite crown restoration material, comprising the following steps: S1: freeze-casting nano-zirconia particles using freeze-casting technology (water is used as the solvent in the freeze-casting slurry, and the nano-zirconia content is 55wt%) and sintering to obtain a TZP scaffold with sufficient strength; S2: Add the TZP scaffold dried in step S1 to a 2L dry glass reactor equipped with mechanical stirring and nitrogen flow. Then, using the Friedel-Crafts reaction principle, terephthaloyl chloride, isophthaloyl chloride, and diphenyl ether as raw materials, aluminum oxide as a catalyst, and 1,2-dichloroethane as a solvent, generate PEAK at room temperature, atmospheric pressure, and a nitrogen atmosphere. PEAK is polymerized in situ to obtain a TZP / PEAK composite matrix. The mass ratio of TZP scaffold to poly(aryletherketone) in the TZP / PEAK composite matrix is ​​4.6:1. S3: The TZP / PEAK composite substrate was immersed in a 20% hydrogen peroxide solution at 60°C and stirred for 6 h. The substrate was then taken out and washed with RO water and dried in an oven at 60°C. The substrate was irradiated with an ultraviolet high-pressure mercury lamp for 1 h to obtain hydroxyl modification on the surface of the TZP / PEAK composite substrate. S4: The hydroxyl-modified composite material was placed in a mixed solution of APTES / anhydrous ethanol (volume ratio 1:10) at 80 °C for 12 h. After the reaction, it was washed with anhydrous ethanol and then dried.

[0033] S5: Weigh 200 mg of Arg, 690 mg of EDC, and 486 mg of HOBT, and add them sequentially into a DIPEA / DMF (volume ratio 1:25) mixed solution to obtain a mixed solution with an Arg concentration of 80 mg / ml. Immerse the APTES-grafted composite material in the mixed solution and place it under gentle stirring for 24 h. After the reaction is completed, wash it twice with anhydrous DMF, three times with RO water, and dry it to obtain an arginine-modified composite material, namely, the AMEM composite material.

[0034] The AMEM composite material prepared above was observed, specifically in combination with reference Figure 1-Figure 3 As shown, during the freeze-casting process, the lamellar growth of ice crystals induced the slurry to arrange itself in layers between the ice crystals, resulting in a lamellar structure of the TZP scaffold after freeze-drying and sintering. The in situ polymerized PEAK fully filled the pores of the TZP scaffold, forming an inorganic-organic composite structure with alternating "TZP-PEAK" structures. The surface micromorphology of the composite did not change significantly after Arg grafting. However, energy-dispersive X-ray spectroscopy (EDS) detected the presence of nitrogen on the composite surface, confirming the successful grafting of Arg onto the surface of the TZP / PEAK composite.

[0035] Example 2: This embodiment of the present invention provides a method for preparing an enamel-like composite crown restoration material, comprising the following steps: S1: freeze-casting nano-zirconia particles using freeze-casting technology (water is used as the solvent in the freeze-casting slurry, and the nano-zirconia content is 60wt%) and sintering to obtain a TZP scaffold with sufficient strength; S2: Add the TZP scaffold dried in step S1 to a 2L dry glass reactor equipped with mechanical stirring and nitrogen flow. Then, using the Friedel-Crafts reaction principle, terephthaloyl chloride, isophthaloyl chloride, and diphenyl ether as raw materials, aluminum oxide as a catalyst, and 1,2-dichloroethane as a solvent, generate PEAK at room temperature, atmospheric pressure, and a nitrogen atmosphere. PEAK is polymerized in situ to obtain a TZP / PEAK composite matrix. The mass ratio of TZP scaffold to poly(aryletherketone) in the TZP / PEAK composite matrix is ​​5.7:1. S3: The TZP / PEAK composite substrate was immersed in a 15% hydrogen peroxide solution at 50°C and stirred for 4 h. The substrate was then taken out, washed with RO water, and dried in an oven at 50°C. The substrate was irradiated with an ultraviolet high-pressure mercury lamp for 0.8 h to obtain hydroxyl modification on the surface of the TZP / PEAK composite substrate. S4: The hydroxyl-modified composite material was placed in a mixed solution of APTES / anhydrous ethanol (volume ratio 1:8) at 70 °C for 10 h. After the reaction, it was washed with anhydrous ethanol and then dried.

[0036] S5: Weigh 200 mg of Arg, 690 mg of EDC, and 486 mg of HOBT, and add them sequentially into a DIPEA / DMF (volume ratio 1:20) mixed solution to obtain a mixed solution with an Arg concentration of 20 mg / ml. Immerse the APTES-grafted composite material in the mixed solution and place it under gentle stirring for 20 h. After the reaction is completed, wash it twice with anhydrous DMF, three times with RO water, and dry it to obtain an arginine-modified composite material, namely, the AMEM composite material.

[0037] Example 3: This embodiment of the present invention provides a method for preparing an enamel-like composite crown restoration material, comprising the following steps: S1: freeze-casting nano-zirconia particles using freeze-casting technology (water is used as the solvent in the freeze-casting slurry, and the nano-zirconia content is 50wt%) and sintering to obtain a TZP scaffold with sufficient strength; S2: Add the TZP scaffold dried in step S1 to a 2L dry glass reactor equipped with mechanical stirring and nitrogen flow. Then, using the Friedel-Crafts reaction principle, terephthaloyl chloride, isophthaloyl chloride, and diphenyl ether as raw materials, aluminum oxide as a catalyst, and 1,2-dichloroethane as a solvent, generate PEAK at room temperature, atmospheric pressure, and a nitrogen atmosphere. PEAK is polymerized in situ to obtain a TZP / PEAK composite matrix. The mass ratio of TZP scaffold to poly(aryletherketone) in the TZP / PEAK composite matrix is ​​2.9:1. S3: The TZP / PEAK composite substrate was immersed in a 25% hydrogen peroxide solution at 60°C and stirred for 8 h. The substrate was then taken out and washed with RO water and dried in an oven at 70°C. The substrate was irradiated with an ultraviolet high-pressure mercury lamp for 1.2 h to obtain hydroxyl modification on the surface of the TZP / PEAK composite substrate. S4: The hydroxyl-modified composite material was placed in a 90°C condensed reflux APTES / anhydrous ethanol (volume ratio 1:12) mixed solution for reaction for 14 h. After the reaction, it was washed with anhydrous ethanol and then dried.

[0038] S5: Weigh 200 mg of Arg, 690 mg of EDC, and 486 mg of HOBT, and add them sequentially into a DIPEA / DMF (volume ratio 1:30) mixed solution to obtain a mixed solution with an Arg concentration of 40 mg / ml. Immerse the APTES-grafted composite material in the mixed solution and place it under gentle stirring for 30 h. After the reaction is completed, wash it twice with anhydrous DMF, three times with RO water, and dry it to obtain an arginine-modified composite material, namely, the AMEM composite material.

[0039] Example 4: This embodiment of the present invention provides a method for preparing an enamel-like composite crown restoration material. The difference from Example 1 is that a mixed solution with an Arg concentration of 60 mg / ml is prepared in S5, and the remaining steps are the same.

[0040] Example 5: This embodiment of the present invention provides a method for preparing an enamel-like composite crown restoration material. The difference from Example 1 is that a mixed solution with an Arg concentration of 100 mg / ml is prepared in S5, and the remaining steps are the same.

[0041] Example 6: This embodiment of the present invention provides a method for preparing an enamel-like composite crown restoration material. The difference from Example 1 is that a mixed solution with an Arg concentration of 120 mg / ml is prepared in S5, and the remaining steps are the same.

[0042] Comparative Example 1: A method for preparing a composite crown restoration material is provided, comprising the following: S1: freeze-cast nano-zirconia particles using freeze-casting technology (water is used as the solvent in the freeze-casting slurry, and the nano-zirconia content is 55wt%) and sintered to obtain a TZP scaffold with sufficient strength (nano-zirconia content is 55wt%); S2: Add the TZP scaffold dried in step S1 to a 2L dry glass reactor equipped with mechanical stirring and nitrogen flow. Then, using the Friedel-Crafts reaction principle, terephthaloyl chloride, isophthaloyl chloride, and diphenyl ether as raw materials, aluminum oxide as a catalyst, and 1,2-dichloroethane as a solvent, generate PEAK at room temperature, atmospheric pressure, and a nitrogen atmosphere. PEAK is polymerized in situ to obtain a TZP / PEAK composite matrix. The mass ratio of TZP scaffold to poly(aryletherketone) in the TZP / PEAK composite matrix is ​​4.6:1. S3: The TZP / PEAK composite matrix was immersed in a 20% hydrogen peroxide solution at 60°C and stirred for 6 h. It was then taken out, washed with RO water, and dried in an oven at 60°C. It was irradiated with an ultraviolet high-pressure mercury lamp for 1 h to modify the surface of the TZP / PEAK composite matrix with hydroxyl groups to obtain a composite crown restoration material.

[0043] Comparative Example 2: A method for preparing a composite crown restoration material is provided, comprising the following: S1: freeze-casting nano-zirconia particles using freeze-casting technology (water is used as the solvent in the freeze-casting slurry, and the nano-zirconia content is 55wt%) and sintering to obtain a TZP scaffold with sufficient strength; S2: Add the TZP scaffold dried in step S1 to a 2L dry glass reactor equipped with mechanical stirring and nitrogen flow. Then, using the Friedel-Crafts reaction principle, terephthaloyl chloride, isophthaloyl chloride, and diphenyl ether as raw materials, aluminum oxide as a catalyst, and 1,2-dichloroethane as a solvent, generate PEAK at room temperature, atmospheric pressure, and a nitrogen atmosphere. PEAK is polymerized in situ to obtain a TZP / PEAK composite matrix. The mass ratio of TZP scaffold to poly(aryletherketone) in the TZP / PEAK composite matrix is ​​4.6:1. S3: The composite material was placed in a mixed solution of APTES / anhydrous ethanol (volume ratio 1:10) under condensation reflux at 80 °C for 12 h. After the reaction, it was washed with anhydrous ethanol and then dried.

[0044] S4: Weigh 200 mg of Arg, 690 mg of EDC, and 486 mg of HOBT, and add them sequentially into a DIPEA / DMF (volume ratio 1:25) mixed solution to obtain a mixed solution with an Arg concentration of 80 mg / ml. Immerse the composite material grafted with APTES in the mixed solution and place it under gentle stirring for 24 h. After the reaction is completed, wash it twice with anhydrous DMF, three times with RO water, and dry it to obtain a composite crown restoration material.

[0045] Comparative Example 3: A method for preparing a composite crown restoration material is provided, comprising the following: S1: freeze-cast nano-zirconia particles using freeze-casting technology (water is used as the solvent in the freeze-casting slurry, and the nano-zirconia content is 55wt%) and sintered to obtain a TZP scaffold with sufficient strength (nano-zirconia content is 55wt%); S2: Add the TZP scaffold dried in step S1 to a 2L dry glass reactor equipped with mechanical stirring and nitrogen flow. Then, using the Friedel-Crafts reaction principle, terephthaloyl chloride, isophthaloyl chloride, and diphenyl ether as raw materials, aluminum oxide as a catalyst, and 1,2-dichloroethane as a solvent, generate PEAK at room temperature, atmospheric pressure, and a nitrogen atmosphere. PEAK is polymerized in situ to obtain a TZP / PEAK composite matrix. The mass ratio of TZP scaffold to poly(aryletherketone) in the TZP / PEAK composite matrix is ​​4.6:1. S3: Weigh 200 mg of Arg and add it to a DIPEA / DMF (volume ratio 1:25) mixed solution to obtain a mixed solution with an Arg concentration of 80 mg / ml. Immerse the composite material synthesized in S2 in the mixed solution and place it under gentle stirring for 24 hours. After the reaction is completed, wash it twice with anhydrous DMF, wash it three times with RO water, and dry it to obtain a composite crown restoration material.

[0046] Test results 1. The performance of the AMEM composite material prepared in Example 1 was tested, with the zirconia and PEAK prepared by cutting as controls. The test method and test results are as follows: The test method is as follows: After the sample is embedded in self-curing dental tray powder and dental tray water, the test surface is polished using a grinder, polishing disk, and polishing liquid until there are no obvious scratches under a light microscope. Ultrasonic cleaning is performed for 10 minutes and then dried for use. The loading, holding, and unloading times of the nanoindentation experiment are all 20 seconds, and the maximum load is 6000 μN. The load-displacement curve is recorded, and the elastic modulus and surface hardness are calculated using HYSITRON TriboScan software. Three areas of each sample are randomly selected for testing, and three samples are tested in each group. The elastic modulus and hardness test results (mean ± variance) of each group of materials are shown in Table 1: Table 1 Test Results of Elastic Modulus and Hardness (Mean ± Variance) Material Young's modulus (GPa) Nanohardness (GPa) TZP 178.37±6.40 13.61±1.25 AMEM 198.45±6.40 14.69±0.90 <![CDATA[ZrO2]]> 233.94±8.27 16.37±0.83 PEAK 5.89±0.06 0.29±0.02 2. The fretting wear performance of the AMEM composite material prepared in Example 1 was detected, and the test methods and results are as follows: After the material was polished to a mirror finish, a spherical fretting wear test was carried out. After 10 4 chewing cycles, the wear amount of its mating interface was measured and analyzed by a white light confocal three-dimensional surface profiler, and the surface friction coefficient calculated by a micro-vibration dynamics tester was referred to. As shown in Figure 4-Figure 8 , it was found that the wear amounts among the materials in each group were: zirconia < glass ceramic < enamel < AMEM < PEAK, and the AMEM composite material had a tribological coefficient similar to that of enamel. In addition, abrasive particles accumulated on the surfaces of zirconia, glass ceramic and PEAK, showing a bulging phenomenon. It can be inferred that with the increase of chewing cycle times, the mismatch of the mating interface will be aggravated. However, compared with other materials, AMEM had less abrasive particle accumulation on the surface and showed fretting wear characteristics similar to those of enamel, which was beneficial to reducing enamel damage, realizing the protection of enamel, and reducing the occurrence of fretting friction wear. Therefore, compared with other common clinical repair and reconstruction materials, arginine grafted on the surface of the TZP / PEAK composite material can reduce the friction coefficient to the greatest extent, reduce enamel damage, realize the protection of enamel, and reduce the occurrence of fretting friction wear.

[0047] 3. The biocompatibility of the AMEM composite materials prepared in Examples 1-6 and the composite crown repair materials prepared in Comparative Examples 1-3 was detected, and the test methods and results are as follows: Morphology and distribution of HGFs: The sterilized materials were placed in a 48-well plate and seeded at a density of 1.5×10 4 cells / well for co-culture of HGFs and the materials. After culturing in a cell incubator for 24 h, the culture medium was removed, washed twice with PBS solution, fixed with glutaraldehyde at 4 °C for 4 h, washed twice with PBS solution, each time for 5 min. Dehydration was carried out with anhydrous ethanol / distilled water solution at volume fraction gradients of 30%, 50%, 75%, 85%, 95%, and 100%, with each gradient dehydration for 10 min. After dehydration, it was air-dried at room temperature. The dried materials were adhered to the SEM sample stage with conductive glue, with the side with cells on the material surface facing up, sputtered with gold in a vacuum sputtering machine for 3 min, and then placed in the SEM sample chamber. Observation and image recording were carried out using SEM under high vacuum and a voltage of 15 kV. The results are as shown in Figures 9-18 , Figure 29 and Figure 30 , and there was no obvious difference in the growth and distribution of HGFs from the control group.

[0048] 4. The anti-Streptococcus mutans properties of the AMEM composite materials prepared in Examples 1-6 and the composite crown restoration materials prepared in Comparative Examples 1-3 were tested. The test methods and test results are as follows: The form and distribution of Sm: The morphology and distribution of bacteria on the surface of the material were observed using SEM. The material processing and bacterial inoculation were the same as above, and Streptococcus mutans was co-cultured with the material. After culturing in the incubator for 24 hours, the culture medium was removed, and the material was washed twice with PBS solution, fixed with glutaraldehyde at 4°C for 4 hours, and washed twice with PBS solution, each time for 5 minutes. Dehydrated with anhydrous ethanol / double-distilled water solution in a gradient of 30%, 50%, 75%, 85%, 95%, and 100% volume fraction, and dehydrated for 10 minutes per gradient. After dehydration, it was dried at room temperature. The dried material was glued to the SEM sample stage with conductive glue, with the bacterial side of the material surface facing up, and sprayed with gold in a vacuum sputtering machine for 3 minutes, then placed in the SEM sample box, and observed and recorded using SEM under high vacuum and 15kV voltage. The results are shown in the figure. Figures 19-28 、 Figure 31 and Figure 32 As shown, the number of bacteria on the surface of the AMEM group is small, and no obvious biofilm is formed. The number of bacteria on the surface of the composite materials in Comparative Examples 2 and 3 is more than that in the AMEM group, and the Arg grafting is insufficient, and a stable antibacterial effect cannot be exerted.

[0049] Mechanical experiments have shown that AMEM has mechanical properties that match well with tooth enamel; micro-friction and wear tests have shown that AMEM has a smaller friction coefficient and less enamel damage, confirming that the material has good lubrication and enamel protection effects; cell experiments have shown that AMEM has good biocompatibility; bacterial experiments have shown that AMEM has good anti-caries bacteria properties, can resist the formation of caries-causing biofilms, and has the best comprehensive performance.

[0050] In summary, AMEM has mechanical properties that match those of tooth enamel, reducing damage to interproximal tooth enamel in terms of mechanical matching and micro-friction wear, and can also have anti-cariogenic properties, regulate the surface microenvironment of the material, and while the biofilm plays a lubricating role, prevent the side effects of increased wear caused by demineralization and roughening of the enamel surface due to the acid erosion of cariogenic bacteria, and can prevent interproximal enamel damage and the occurrence of food impaction.

[0051] In general, the embodiments of the present invention focus on the biomechanical mechanism of food impaction after fixed restoration and reconstruction, and innovatively attribute the initiating factors of food impaction after restoration to the results of the coupled interaction of mechanical, biological and synergistic composite micro-wear between the tooth adjacent parts. This breaks through the limitations of previous dental wear research that only focuses on the occlusal surface and biofilm-related research often ignores its mechanical effects. It integrates the two perspectives of bio-mechanics, constructs the biological compatibility and mechanical compatibility of interproximal restoration materials, and the coupled interaction mechanism of the synergistic effect of the two on the stability and loss of tooth adjacent relationships; innovatively synthesizes AMEM crown restoration materials that are biomimetic with the organic and inorganic phase structures of natural enamel and have the ability to regulate the microecology of the adjacent parts.

[0052] In this embodiment, hydroxyl groups are introduced onto the surfaces of TZP and PEAK, and arginine is grafted onto the surface using APTES as an intermediate. Arginine is rich in carboxyl groups, and covalent bonds are designed to ensure a stable and strong bond between arginine and the composite material surface. Arginine is grafted onto the composite material surface to achieve specific surface modification of organic-inorganic materials. Arginine can be grafted onto the specific interface of organic-inorganic materials at varying concentrations, with 80 mg / ml being the optimal concentration, to regulate the biofilm microenvironment.

[0053] The embodiments of the present invention compare and study the mechanical-biological matching advantages of existing restorative materials, providing a cognitive basis for the future research and development and selection of new proximal restorative materials and the tribological design of tooth joints, which is scientific and pioneering.

[0054] The bionic crown restoration material prepared in the embodiment of the present invention, which is adapted to the bio-mechanical properties of tooth enamel, can simultaneously achieve matching with the biological and mechanical properties of tooth enamel, can regulate the microecological environment on the surface of the material, and ultimately achieve anti-fretting wear effect, which is beneficial to reduce the loss of adjacent joints and prevent the occurrence of food impaction.

[0055] The specific implementation methods described above further illustrate the objectives, technical solutions and beneficial effects of the present invention in detail. It should be understood that the above description is only a specific implementation method of the present invention and is not intended to limit the scope of protection of the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.

Claims

1. An imitation enamel composite crown repair material, characterized in that: It comprises a composite matrix, a reticular wrapping structure and arginine, wherein the reticular wrapping structure is coated on the outside of the composite matrix, and the arginine is grafted onto the reticular wrapping structure; The composite matrix includes a TZP support and polyaryletherketone.

2. The imitation enamel composite crown restoration material according to claim 1, characterized in that: The TZP scaffold and the polyaryletherketone are arranged in alternating layers, and the mass ratio of the TZP scaffold to the polyaryletherketone in the composite matrix is ​​2.9-5.7:

1.

3. The imitation enamel composite crown restoration material according to claim 2, characterized in that: The network wrapping structure is formed by covalently bonding one side of the siloxane hydrolyzed by γ-aminopropyltriethoxysilane to the hydroxyl group on the surface of the composite matrix, and the amino group on the other side of the network wrapping structure can undergo a condensation reaction with the carboxyl group of arginine to complete grafting and coating.

4. The imitation enamel composite crown restoration material according to claim 3, characterized in that: The hydroxyl groups on the surface of the composite matrix include hydroxyl groups on the TZP support and hydroxyl groups on the surface of the polyaryletherketone; The hydroxyl groups on the TZP scaffold are formed by functionalizing the TZP scaffold with H2O2; The hydroxyl groups on the surface of the polyaryletherketone are formed by irradiating the polyaryletherketone with UV light.

5. A method for preparing the imitation enamel composite crown repair material according to any one of claims 1 to 4, characterized in that: The following steps are involved: S1: freeze-casting nano-zirconia particles and sintering them to obtain a TZP scaffold, wherein the TZP particles account for 50-60 wt% of the freeze-cast slurry; S2: adding TZP scaffold, generating poly(aryletherketone) by Friedel-Crafts reaction principle, achieving in situ polymerization of poly(aryletherketone) to obtain TZP / PEAK composite matrix; S3: immersing the TZP / PEAK composite matrix in a hydrogen peroxide solution, stirring, taking it out, and then washing and drying it in sequence; Then, UV light was applied to modify the surface of the TZP / PEAK composite matrix with hydroxyl groups. S4: placing the hydroxyl-modified TZP / PEAK composite matrix in a mixed solution of γ-aminopropyltriethoxysilane and anhydrous ethanol for reaction, and washing with anhydrous ethanol and drying after the reaction to obtain a composite material grafted with APTES; S5: Weigh arginine, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide and 1-hydroxybenzotriazole and add them in turn to a mixed solution of diisopropylethylamine and dimethylformamide to obtain a mixed solution containing arginine, immerse the composite material grafted with APTES in the mixed solution containing arginine to react, and after the reaction is completed, wash and dry in sequence to obtain an AMEM composite material.

6. The method for preparing an imitation enamel composite crown restoration material according to claim 5, characterized in that: The method described in S2 utilizes the Friedel-Crafts reaction principle to generate polyaryletherketone, including using terephthaloyl chloride, isophthaloyl chloride and diphenyl ether as raw materials, aluminum oxide as a catalyst and 1,2-dichloroethane as a solvent for polymerization reaction.

7. The method for preparing an imitation enamel composite crown restoration material according to claim 5, characterized in that: The concentration of the hydrogen peroxide solution in S3 is 15-25%, the stirring temperature is 50-60° C., the stirring time is 4-8 hours, and the UV irradiation time is 0.8-1.2 hours.

8. The method for preparing an imitation enamel composite crown restoration material according to claim 5, characterized in that: The volume ratio of γ-aminopropyltriethoxysilane to anhydrous ethanol in S4 is 1:8-12, the reaction temperature is 70-90° C., and the reaction time is 10-14 hours.

9. The method for preparing an imitation enamel composite crown restoration material according to claim 5, characterized in that: The concentration of arginine in the mixed solution containing arginine in S5 is 70-90 mg / ml, the reaction time is 20-30 hours, and the washing step includes washing with anhydrous DMF at least twice and washing with deionized water at least three times.

10. A use of the imitation enamel composite crown restoration material according to any one of claims 1 to 4, characterized in that: The method comprises using the material to prepare a dental restoration, wherein the dental restoration comprises at least one of a fixed / implanted dental crown, a dental bridge, and a dental veneer.

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