An enamel-like composite crown restoration material and a preparation method and application thereof

Abstract

The application discloses an enamel-like composite crown restoration material and a preparation method and application thereof, relates to the field of ceramic oral restoration, and relates to a restoration material which comprises a composite base, a net-like wrapping structure and arginine, wherein the net-like wrapping structure is coated on the outer side of the composite base, and the arginine is grafted on the net-like wrapping structure; and the composite base comprises a TZP support and a polyaryletherketone. The application provides the composite base which is matched with the mechanical properties of tooth enamel, and successfully grafts the arginine on the outer side of the composite base by means of the net-like wrapping structure, so that the arginine is stably grafted on the special interface of the organic-inorganic composite material, and the special target surface modification of the organic-inorganic material is realized.

Description

Technical Field

[0001] This invention relates to the field of ceramic dental restoration, specifically to a enamel-like composite crown restoration material, its preparation method, and its application. Background Technology

[0002] In the field of dentistry, food impaction has a high incidence rate and is a common complication after restorative and reconstructive procedures. The hardness of the occlusal surface of human tooth enamel is approximately 4.6-5.5 GPa, with an elastic modulus of approximately 94 GPa, while the hardness of the proximal surface is approximately 4.0-4.7 GPa, with an elastic modulus of approximately 80 GPa. However, commonly used restorative and reconstructive materials, such as single-layer zirconia, have a hardness of 11.7-13.7 GPa and an elastic modulus of 200 GPa, far exceeding that of tooth enamel. This indicates a significant mismatch in mechanical properties between restorative and reconstructive materials and tooth enamel. When the oral cavity performs chewing functions, in addition to the cyclical contact between the occlusal surfaces, micro-motion contact also occurs between adjacent teeth due to the physiological mobility of natural teeth, and occlusal forces are transmitted through these contact points. The greater the mismatch in mechanical properties between natural teeth and restorative materials, the greater the micro-motion wear at the interface, leading to loss of contact and increasing the likelihood of food impaction.

[0003] The proximal area is not in close contact; there are tiny gaps of 3-21 μm 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 proximal area, 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 produce acid through metabolism, which leads to demineralization of hard tissue, resulting in a rough surface and even caries. This will aggravate the micro-motion wear at the proximal area 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 application is still limited by their fracture sensitivity and relative tooth wear. The polyaryletherketone (PAEK) family of specialty engineering plastics has become a hot topic in international dentistry in recent years due to its chemical stability, wear resistance, thermoplasticity, biocompatibility, aesthetic advantages, and radiolucent properties. PAEK possesses good thermal stability, excellent mechanical properties, and biocompatibility, making it a promising material for dental materials. However, pure PAEK has an elastic modulus of only about 5 GPa, which is insufficient in mechanical properties, limiting its clinical application.

[0005] Currently, conventional crown restoration materials still have drawbacks such as poor biomechanical compatibility with tooth enamel and poor micro-motion abrasion resistance.

[0006] Enamel has two unique microstructure characteristics: 1, the controlled nucleation and regular growth of nanoscale hydroxyapatite (HA) crystals form a micrometer-scale three-dimensional structure; 2, the organic component fills the gap outside the inorganic component, and the two combine to form a regularly arranged macrostructure. This naturally formed multi-level structure enables natural enamel to have a unique fracture toughening mechanism. The natural and ingenious structure of natural enamel can provide inspiration for the biomimetic design of repair materials. The inorganic part of the repair material provides a hard scaffold, and the organic filling gives the bone toughness and ductility. The combination of inorganic and organic substances in the biomimetic structure can give the material high yield strength and fracture toughness, and has great application potential in the replacement treatment of tooth defects / loss.

[0007] Arginine (Arg) is an amino acid present in human saliva and is an important hub for regulating the acid-base balance and microecological balance of dental plaque. Alkaline-producing bacteria in the oral cavity can use the arginine deiminase system to rapidly metabolize free arginine in the biofilm into ammonia, thereby buffering acidic products and regulating the pH of the biofilm, protecting the acid-intolerant flora in the biofilm, and maintaining the non-cariogenic state of the flora in the biofilm. Exogenous arginine can be taken up and metabolized by bacteria in the biofilm, improving the cariogenic state of the biofilm. In addition, long-term exogenous arginine can stabilize the pH of the microecological environment, reduce the activity of cariogenic bacteria, reduce the formation of cariogenic biofilm, and regulate the microenvironment on the tooth crown surface.

[0008] Arginine grafting has an interface functionalization bottleneck: arginine cannot be stably grafted, physical adsorption is easy to fall off, and long-term protection cannot be achieved. Covalent bonding is needed to obtain stable arginine grafting, but arginine needs to be covalently combined with amino or carboxyl groups through condensation reaction. However, organic-inorganic matrix materials lack active groups, and the special interface of the organic-inorganic composite material needs to be further modified.

[0009] In view of this, the present application is proposed. SUMMARY

[0010] The purpose of the present application is to provide an enamel-like composite crown repair material and a preparation method and application thereof. By providing a composite matrix matched with the mechanical properties of tooth enamel, arginine is successfully grafted on the outside of the composite matrix through a reticular wrapping structure, thereby solving the problem that arginine cannot be stably grafted in the prior art.

[0011] Firstly, the enamel-like composite crown repair material provided by the embodiments of the present application comprises a composite matrix, a reticular wrapping structure and arginine, the reticular wrapping structure is wrapped on the outside of the composite matrix, and the arginine is grafted on the reticular wrapping structure.

[0012] The composite matrix comprises a TZP scaffold and a polyaryletherketone.

[0013] As an optional implementation, the TZP support and the polyaryletherketone are arranged in an alternating layer, and the mass ratio of the TZP support and the polyaryletherketone in the composite matrix is 2.9-5.7:1.

[0014] As an optional implementation, the net-like wrapping structure is formed by covalent bond combination of one side of siloxane hydrolysis of gamma-aminopropyl triethoxysilane and the hydroxyl on the surface of the composite matrix, and the other side of the net-like wrapping structure is capable of condensation reaction with the carboxyl of arginine to complete grafting and coating.

[0015] As an optional implementation, the hydroxyl on the surface of the composite matrix includes the hydroxyl on the TZP support and the hydroxyl on the surface of the polyaryletherketone.

[0016] The hydroxyl on the TZP support is formed after the TZP support is functionalized by H2O2.

[0017] The hydroxyl on the surface of the polyaryletherketone is formed after the polyaryletherketone is irradiated by UV light.

[0018] Secondly, the embodiment of the present application also provides a preparation method of the enamel-like composite crown restoration material, which comprises the following steps:

[0019] S1: nano-zirconia particles are frozen and cast into shape and sintered by a frozen casting technology to obtain a TZP support, which simulates the rigidity of the inorganic phase of enamel; wherein the proportion of the TZP particles in the frozen casting slurry used is 50-60 wt%.

[0020] S2: the TZP support is added, and polyaryletherketone is generated by using the principle of Friedel-Crafts reaction to realize in-situ polymerization of the polyaryletherketone, so as to obtain a TZP / PEAK composite matrix, and the composite modulus tends to be close to the elastic modulus of enamel.

[0021] S3: the TZP / PEAK composite matrix is immersed in a hydrogen peroxide solution and taken out after stirring, and then is sequentially cleaned and dried; then, UV light is irradiated to obtain hydroxyl modification on the surface of the TZP / PEAK composite matrix, that is, two-step hydroxyl modification is performed;

[0022] S4: the TZP / PEAK composite matrix with completed hydroxyl modification is placed in a mixed solution of gamma-aminopropyl triethoxysilane and anhydrous ethanol for reaction, and after the reaction is completed, the composite material grafted with APTES is obtained by cleaning with anhydrous ethanol and drying, that is, APTES is covalently combined to the interface through siloxane bond.

[0023] S5: arginine, 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide and 1-hydroxybenzotriazole are weighed into a mixed solution of diisopropylethylamine and dimethylformamide in sequence to obtain a mixed solution containing arginine, and the composite material grafted with APTES is immersed in the mixed solution containing arginine for reaction, and after the reaction is completed, cleaning and drying are sequentially performed to obtain an AMEM composite material. This step specifically covalently grafts arginine to the exposed amino group of APTES through an amide bond in the presence of an activating agent EDC / HOBT to obtain an arginine microecological regulation enamel composite material (AMEM).

[0024] As an optional implementation, the polyaryletherketone is generated by using the Friedel-Crafts reaction principle in S2, including using terephthaloyl chloride, isophthaloyl chloride and diphenyl ether as raw materials, aluminum trioxide as a catalyst, and 1,2-dichloroethane as a solvent for polymerization reaction.

[0025] As an optional implementation, the concentration of the hydrogen peroxide solution in S3 is 15-25%, the stirring temperature is 50-60℃, the stirring time is 4-8 hours, and the UV light irradiation time is 0.8-1.2 hours.

[0026] As an optional implementation, the volume ratio of γ-aminopropyl triethoxysilane to anhydrous ethanol in S4 is 1:8-12, the reaction temperature is 70-90℃, and the reaction time is 10-14 hours.

[0027] As an optional implementation, the concentration of arginine in the mixed solution containing arginine in S5 is 70-90 mg / ml, the reaction time is 20-30 hours, the cleaning step includes cleaning with anhydrous DMF at least twice and cleaning with deionized water at least three times. It should be noted that the arginine grafting concentration is not limited, and preferably 80 mg / ml.

[0028] Finally, the embodiment of the present application also provides an application of the enamel composite crown restoration material, which comprises using the material to prepare a dental restoration body, and the dental restoration body comprises at least one of a fixed / implanted dental crown, a dental bridge and a dental veneer.

[0029] Compared with the prior art, the embodiment of the present application has the following advantages and beneficial effects:

[0030] 1、The embodiment of the present application successfully grafts arginine on the outside of the composite substrate by means of the reticular wrapping structure, so as to achieve the purpose of grafting arginine on the special interface of the organic-inorganic composite material and realize the special target surface modification of the organic-inorganic material.

[0031] 2、The synthetic enamel-like crown restoration material in the embodiment of the present application shows the elastic modulus and hardness matching with the tooth enamel, and has excellent strength, elastic-plasticity characteristics, reduces the enamel micro-attrition caused by the mechanical mismatch, compared with the commonly used materials, has no significant influence on the cytotoxicity in the in-vitro test, and has good biocompatibility in the in-vivo study.

[0032] 3、The embodiment of the present application adopts the process of "two-step hydroxylation (H2O2 oxidation TZP+UV activation PAEK) -> silane coupling bridging (APTES) -> arginine covalent grafting", arginine is stably grafted at the special interface of the organic-inorganic composite material, the special target surface modification of the organic-inorganic material is realized, the grafted arginine is metabolized to ammonia by oral bacteria, the pH of the biofilm is adjusted to a non-cariogenic state, the formation of the cariogenic biofilm is reduced, the cariogenic bacterial activity is inhibited, the microenvironment of the crown surface is adjusted, the enamel demineralization and roughening are prevented, and the healthy biofilm lubrication and the base body wear reduction performance are cooperatively protected to the adjacent enamel.

[0033] 4、The biomimetic crown restoration material prepared in the embodiment of the present application is adapted to the biological and mechanical properties of tooth enamel, simultaneously realizes the matching with the biological and mechanical properties of tooth enamel, finally realizes the anti-micro-attrition effect, is beneficial to reducing the loss of the adjacent tooth, and prevents the occurrence of food impaction. The micro-attrition of the enamel at the adjacent tooth and the interaction of the biofilm on the micro-attrition of the enamel at the adjacent tooth are analyzed, the work is further carried out from the aspects of the anti-caries function of the material, the reduction of the micro-attrition of the enamel at the adjacent interface, the non-cariogenic metabolic state of the biofilm at the adjacent interface, and the synergistic wear reduction effect of the two, the long-term preservation of the adjacent tooth tissue synchronous with the aging change of the natural tooth is further realized, finally, the biological tribology design principles and measures for enhancing the long-term stability of the adjacent tooth and preventing and treating food impaction are proposed, and cognitive basis is provided for the research and development of a new type of adjacent tooth restoration material. BRIEF DESCRIPTION OF DRAWINGS

[0034] In order to more clearly illustrate the technical solutions of the example embodiments of the present application, the following will briefly introduce the drawings needed to be used in the embodiments. It should be understood that the following drawings only show some embodiments of the present application, and therefore should not be regarded as a limitation on the scope. For those skilled in the art, other related drawings can also be obtained without creative labor. In the drawings:

[0035] Figure 1 SEM diagram of the AMEM composite material prepared for embodiment 1;

[0036] wherein Figure 1 b is Figure 1 a is a local enlarged view;

[0037] Figure 2Elemental mapping of the surface of the AMEM composite prepared in Example 1;

[0038] wherein Figure 2 a 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 d;

[0039] Figure 3 Energy spectrum of the AMEM composite prepared in Example 1;

[0040] Figure 4 Figure 10 is a surface topography of enamel after 10 4 mastication cycles tangential fretting wear;

[0041] Figure 5 Figure 10 is a surface topography of AMEM after 10 4 mastication cycles tangential fretting wear;

[0042] Figure 6 Figure 10 is a surface topography of zirconia after 10 4 mastication cycles tangential fretting wear;

[0043] Figure 7 Figure 10 is a surface topography of glass-ceramic after 10 4 mastication cycles tangential fretting wear;

[0044] Figure 8 Figure 10 is a surface topography of PEAK after 10 4 mastication cycles tangential fretting wear;

[0045] Figure 9 Figure 10 is an electron micrograph of HGFs co-cultured with the AMEM composite prepared in Example 2 for 24 h, Figure 9 b is Figure 9 a;

[0046] Figure 10 Figure 10 is an electron micrograph of HGFs co-cultured with the AMEM composite prepared in Example 3 for 24 h, Figure 10 b is Figure 10 a;

[0047] Figure 11 Figure 10 is an electron micrograph of HGFs co-cultured with the AMEM composite prepared in Example 4 for 24 h, Figure 11 b is Figure 11 a;

[0048] Figure 12 The electron micrograph of the AMEM composite material prepared in Example 1 after co-culturing with HGFs for 24h, Figure 12 b is Figure 12 The local enlarged view of a;

[0049] Figure 13 The electron micrograph of the AMEM composite material prepared in Example 5 after co-culturing with HGFs for 24h, Figure 13 b is Figure 13 The local enlarged view of a;

[0050] Figure 14 The electron micrograph of the AMEM composite material prepared in Example 6 after co-culturing with HGFs for 24h, Figure 14 b is Figure 14 The local enlarged view of a;

[0051] Figure 15 The electron micrograph of the TZP scaffold prepared in Example 1 after co-culturing with HGFs for 24h, 15b is Figure 15 The local enlarged view of a;

[0052] Figure 16 The electron micrograph of the composite crown restoration material prepared in Comparative Example 1 after co-culturing with HGFs for 24h, 16b is Figure 16 The local enlarged view of a;

[0053] Figure 17 The electron micrograph of Zr02 after co-culturing with HGFs for 24h, 17b is Figure 17 The local enlarged view of a;

[0054] Figure 18 The electron micrograph of PEAK after co-culturing with HGFs for 24h, 18b is Figure 18 The local enlarged view of a;

[0055] Figure 19 The electron micrograph of the AMEM composite material prepared in Example 2 after co-culturing with Streptococcus mutans for 24h, 19b is Figure 19 The local enlarged view of a;

[0056] Figure 20 The electron micrograph of the AMEM composite material prepared in Example 3 after co-culturing with Streptococcus mutans for 24h, 20b is Figure 20 The local enlarged view of a;

[0057] Figure 21 The electron micrograph of the AMEM composite material prepared in Example 4 after co-culturing with Streptococcus mutans for 24h, 21b is Figure 21a is a partial enlarged view of;

[0058] Figure 22 Fig. 22b is an electron microscope photo of S. mutans co-cultured with the AMEM composite material prepared in Example 5 for 24 h; Figure 22 a is a partial enlarged view of;

[0059] Figure 23 Fig. 23b is an electron microscope photo of S. mutans co-cultured with the AMEM composite material prepared in Example 6 for 24 h; Figure 23 a is a partial enlarged view of;

[0060] Figure 24 Fig. 24b is an electron microscope photo of S. mutans co-cultured with the AMEM composite material prepared in Example 6 for 24 h; Figure 24 a is a partial enlarged view of;

[0061] Figure 25 Fig. 25b is an electron microscope photo of S. mutans co-cultured with the TZP scaffold prepared in Example 1 for 24 h; Figure 25 a is a partial enlarged view of;

[0062] Figure 26 Fig. 26b is an electron microscope photo of S. mutans co-cultured with the composite crown restoration material prepared in Comparative Example 1 for 24 h; Figure 26 a is a partial enlarged view of;

[0063] Figure 27 Fig. 27b is an electron microscope photo of S. mutans co-cultured with Zr02for 24 h; Figure 27 a is a partial enlarged view of;

[0064] Figure 28 Fig. 28b is an electron microscope photo of S. mutans co-cultured with PEAK for 24 h; Figure 28 a is a partial enlarged view of;

[0065] Figure 29 Fig. 29b is an electron microscope photo of HGFs co-cultured with the composite crown restoration material prepared in Comparative Example 2 for 24 h; Figure 29 a is a partial enlarged view of;

[0066] Figure 30 Fig. 30b is an electron microscope photo of HGFs co-cultured with the composite crown restoration material prepared in Comparative Example 3 for 24 h; Figure 30 a is a partial enlarged view of;

[0067] Figure 31 Fig. 31b is an electron microscope photo of S. mutans co-cultured with the composite crown restoration material prepared in Comparative Example 2 for 24 h; Figure 31 a is a partial enlarged view of;

[0068] Figure 32 The electron microscope photos of the complex crown restoration material prepared by the streptococcus mutans and the comparative example 3 after 24h co-culture, 32b is Figure 32 a is a local enlarged view. DETAILED DESCRIPTION

[0069] In order to make the purpose, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions in the embodiments of the present application will be described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present application, rather than all the embodiments.

[0070] Therefore, the detailed description of the embodiments of the present application provided below is not intended to limit the scope of the claimed present application, but only represents selected embodiments of the present application. All other embodiments obtained by those of ordinary skill in the art without creative labor based on the embodiments in the present application are within the scope of protection of the present application.

[0071] The embodiments of the present application provide a preparation method of enamel-like composite crown restoration material, including the following contents:

[0072] S1: obtain a TZP support with sufficient strength by freeze casting nano-zirconia particles (water is used as a solvent in the freeze casting slurry, and the content of nano-zirconia is in the range of 50-60wt%) and sintering after freeze casting;

[0073] S2: in a 2L dry glass reaction kettle equipped with mechanical stirring and nitrogen inlet, the dried TZP support in step S1 is added, then PEAK is generated by using the principle of Friedel-Crafts reaction, using terephthaloyl chloride, isophthaloyl chloride and diphenyl ether as raw materials, using aluminum oxide as catalyst, using 1,2-dichloroethane as solvent, under normal temperature, normal pressure and nitrogen atmosphere. The PEAK is in-situ polymerized to obtain a TZP / PEAK composite matrix, and the mass ratio of the TZP support to the polyaryletherketone in the TZP / PEAK composite matrix is 2.9-5.7:1;

[0074] S3: after being immersed in a 15-25% hydrogen peroxide solution at 50-60℃ for 4-8h and then taken out, the TZP / PEAK composite matrix is cleaned with RO water and then dried in an oven at 50-70℃; the surface of the TZP / PEAK composite matrix is modified with hydroxyl groups by using a UV high-pressure mercury lamp for irradiation for 0.8-1.2h;

[0075] S4: the composite material after the hydroxyl group modification is placed in a 70-90℃ condensation refluxing APTES / anhydrous ethanol (volume ratio 1:8-12) mixed solution for reaction for 10-14h, and then cleaned with anhydrous ethanol and dried after the reaction;

[0076] S5: Arg, EDC and HOBT are weighed and sequentially added into a mixed solution of DIPEA / DMF (volume ratio 1:20~30) to obtain a mixed solution with a concentration of 70~90 mg / ml of Arg, and then the composite material grafted with APTES is immersed in the mixed solution and placed under light stirring for 20~30 h, after the reaction is completed, the composite material is washed with anhydrous DMF for at least twice, washed with RO water for at least three times, and dried to obtain an arginine-modified composite material, i.e., an AMEM composite material.

[0077] In the crown repair material of the embodiment of the present application, after the TZP is treated by H2O2 functionalization, a large number of hydroxyl groups that can be used as reaction sites are introduced; in addition, the carbonyl groups on the surface of the PEAK are converted into hydroxyl groups by UV irradiation; further, the siloxane hydrolyzed from γ-aminopropyl triethoxysilane (APTES) is covalently bonded to the hydroxyl groups on the surface of the composite material to form a reticular wrapping, and condensation reaction occurs between the amino groups at the other end and the carboxyl groups of arginine to complete grafting and coating, so that arginine is stably grafted to the surface of the TZP / PEAK composite material.

[0078] The design of the crown repair material of the embodiment of the present application simultaneously achieves the mechanical properties matching the tooth enamel, good biocompatibility and antibacterial properties, and the synergistic matching of mechanics and biology enhances the matching between the repair material and the tooth enamel to resist micromotion and abrasion. The preparation of the biomimetic ceramic scaffold and the in-situ polymerization technology for toughening the PEAK material are further modified by grafting arginine on the interface surface of the ceramic scaffold-PEAK material to realize the function of regulating the microenvironment of the biological film on the surface of the composite material.

[0079] In order to better reflect the significant effect of the embodiment of the present application, the following will verify the specific embodiments and comparative examples.

[0080] Embodiment 1: The embodiment of the present application provides a preparation method of an enamel-like composite crown repair material, which includes the following contents:

[0081] S1: Nanometer zirconia particles are cold-molded by a cold-molding technology (water is used as a solvent in a cold-molding slurry, and the content of nanometer zirconia is 55wt%) and sintered to obtain a TZP scaffold with sufficient strength;

[0082] S2: In a 2L dry glass reaction kettle equipped with mechanical stirring and nitrogen inlet, the dried TZP scaffold in step S1 is added, then PEAK is generated by using the principle of Friedel-Crafts reaction, using terephthaloyl chloride, isophthaloyl chloride and diphenyl ether as raw materials, using aluminum oxide as a catalyst, and using 1,2-dichloroethane as a solvent, under normal temperature, normal pressure and nitrogen atmosphere. PEAK is in-situ polymerized to obtain a TZP / PEAK composite substrate, and the mass ratio of the TZP scaffold to the polyaryletherketone in the TZP / PEAK composite substrate is 4.6:1.

[0083] S3: The TZP / PEAK composite matrix was immersed in a 20% hydrogen peroxide solution at 60 ℃ and stirred for 6 h. After being taken out, it was washed with RO water and dried in an oven at 60 ℃. The surface of the TZP / PEAK composite matrix was irradiated with a high-pressure mercury lamp for 1 h to obtain hydroxyl modification.

[0084] S4: The hydroxyl-modified composite material was placed in a mixed solution of APTES / anhydrous ethanol (volume ratio 1:10) under reflux at 80 °C and reacted for 12 h. After the reaction was completed, the composite material was washed with anhydrous ethanol and then dried.

[0085] S5: Weigh 200 mg Arg, 690 mg EDC and 486 mg HOBT, and add them sequentially 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 grafted with APTES into the mixed solution and let it stand for 24 h with gentle stirring. After the reaction is complete, wash twice with anhydrous DMF and three times with RO water, and dry to obtain the arginine-modified composite material, namely the AMEM composite material.

[0086] The appearance of the AMEM composite material prepared above was analyzed, and specific details were obtained by referring to the reference. Figures 1-3 As shown, during the freeze casting process, the layered growth of ice crystals induces the slurry to arrange itself in layers between the ice crystals, resulting in a lamellar structure for the freeze-dried and sintered TZP scaffold. In-situ polymerized PEAK fully fills the pores of the TZP scaffold, forming an inorganic-organic composite structure with alternating TZP-PEAK layers. After Arg grafting, the surface microstructure of the composite material did not change significantly. However, energy-dispersive X-ray spectroscopy (EDS) detected the presence of nitrogen on the composite surface, confirming the successful grafting of Arg onto the TZP / PEAK composite surface.

[0087] Example 2: This embodiment of the invention provides a method for preparing an enamel-like composite crown restoration material, comprising the following:

[0088] S1: TZP scaffolds with sufficient strength are obtained by freezing and casting nano-zirconia particles using cryogenic casting technology (water is used as a solvent in the cryogenic casting slurry, and the nano-zirconia content is 60wt%).

[0089] S2: In a 2L dry glass reactor with mechanical stirring and nitrogen, the dried TZP support in step S1 is added, then using the principle of Friedel-Crafts reaction, terephthaloyl chloride, isophthaloyl chloride and diphenyl ether as raw materials, aluminum oxide as catalyst, 1,2-dichloroethane as solvent, under normal temperature, normal pressure, nitrogen atmosphere to generate PEAK. In-situ polymerization of PEAK is realized, and the material is TZP / PEAK composite matrix, and the mass ratio of TZP support to polyaryletherketone in the TZP / PEAK composite matrix is 5.7:1;

[0090] S3: The TZP / PEAK composite matrix is immersed in a 50 ℃ 15 % hydrogen peroxide solution for 4 h, then taken out, washed with RO water, and dried in an oven at 50 ℃; the surface of the TZP / PEAK composite matrix is modified with hydroxyl groups by irradiation with a UV high-pressure mercury lamp for 0.8 h;

[0091] S4: The composite material with completed hydroxyl modification is placed in a 70 ℃ condensation refluxing APTES / anhydrous ethanol (volume ratio 1:8) mixed solution for 10 h, then washed with anhydrous ethanol and dried.

[0092] S5: 200 mg of Arg, 690 mg of EDC and 486 mg of HOBT are weighed and sequentially added into a DIPEA / DMF (volume ratio 1:20) mixed solution to obtain a mixed solution with a concentration of 20 mg / ml of Arg, the APTES grafted composite material is immersed in the mixed solution and placed under light stirring for 20 h, then washed with anhydrous DMF twice, RO water three times, and dried to obtain an arginine modified composite material, namely an AMEM composite material.

[0093] Example 3: The example of the application provides a preparation method of an enamel-like composite crown restoration material, which includes the following contents:

[0094] S1: The nano-zirconia particles are cold-cast into a TZP support by cold casting technology (water is used as a solvent in the cold casting slurry, and the content of nano-zirconia is 50wt%), and the TZP support with sufficient strength is obtained after sintering;

[0095] S2: In a 2L dry glass reactor with mechanical stirring and nitrogen, the dried TZP support in step S1 is added, then using the principle of Friedel-Crafts reaction, terephthaloyl chloride, isophthaloyl chloride and diphenyl ether as raw materials, aluminum oxide as catalyst, 1,2-dichloroethane as solvent, under normal temperature, normal pressure, nitrogen atmosphere to generate PEAK. In-situ polymerization of PEAK is realized, and the material is TZP / PEAK composite matrix, and the mass ratio of TZP support to polyaryletherketone in the TZP / PEAK composite matrix is 2.9:1;

[0096] S3: The TZP / PEAK composite matrix was immersed in a 60℃ 25% hydrogen peroxide solution and stirred for 8h, then taken out, washed with RO water, and dried in an oven at 70℃; the surface of the TZP / PEAK composite matrix was modified with hydroxyl groups by irradiation with a UV high-pressure mercury lamp for 1.2h;

[0097] S4: The hydroxyl-modified composite material was placed in a 90℃ condensing refluxing APTES / anhydrous ethanol (volume ratio 1:12) mixed solution for reaction for 14h, then washed with anhydrous ethanol and dried.

[0098] S5: 200mg Arg, 690mg EDC and 486mg HOBT were weighed and sequentially added to a DIPEA / DMF (volume ratio 1:30) mixed solution to obtain a mixed solution with an Arg concentration of 40mg / ml; the APTES-grafted composite material was immersed in the mixed solution and placed under light stirring for 30h, then washed twice with anhydrous DMF, three times with RO water, and dried to obtain an Arg-modified composite material, namely an AMEM composite material.

[0099] Example 4: The example of the present application provides a preparation method of an enamel-like composite crown restoration material, which is different from example 1 in that a mixed solution with an Arg concentration of 60mg / ml is prepared in S5, and the remaining steps are the same.

[0100] Example 5: The example of the present application provides a preparation method of an enamel-like composite crown restoration material, which is different from example 1 in that a mixed solution with an Arg concentration of 100mg / ml is prepared in S5, and the remaining steps are the same.

[0101] Example 6: The example of the present application provides a preparation method of an enamel-like composite crown restoration material, which is different from example 1 in that a mixed solution with an Arg concentration of 120mg / ml is prepared in S5, and the remaining steps are the same.

[0102] Comparative Example 1: A preparation method of a composite crown restoration material is provided, which includes the following contents:

[0103] S1: A TZP support (nanometer zirconia content 55wt%) with sufficient strength was obtained by freeze casting technology (water as solvent in the freeze casting slurry, nanometer zirconia content 55wt%) to freeze cast and sinter nanometer zirconia particles;

[0104] S2: In a 2L dry glass reactor with mechanical stirring and nitrogen, the dried TZP support in step S1 was added, then using the principle of Friedel-Crafts reaction, terephthaloyl chloride, isophthaloyl chloride and diphenyl ether as raw materials, aluminum oxide as catalyst, 1,2-dichloroethane as solvent, under normal temperature, normal pressure, nitrogen atmosphere to generate PEAK. In-situ polymerization of PEAK was realized, and the material was TZP / PEAK composite matrix, and the mass ratio of TZP support to polyaryletherketone in the TZP / PEAK composite matrix was 4.6:1;

[0105] S3: The TZP / PEAK composite matrix was immersed in a 60 ℃ 20 % hydrogen peroxide solution and stirred for 6 h, then taken out, washed with RO water, and dried in an oven at 60 ℃; the surface of the TZP / PEAK composite matrix was modified with hydroxyl groups by irradiation with a UV high-pressure mercury lamp for 1 h, to obtain a composite crown restoration material.

[0106] Comparative Example 2: A preparation method of a composite crown restoration material was provided, comprising the following contents:

[0107] S1: Nanometer zirconia particles were cold-molded by a cold casting technology (water as solvent in the cold casting slurry, and the content of nanometer zirconia was 55wt%) and sintered to obtain a TZP support with sufficient strength;

[0108] S2: In a 2L dry glass reactor with mechanical stirring and nitrogen, the dried TZP support in step S1 was added, then using the principle of Friedel-Crafts reaction, terephthaloyl chloride, isophthaloyl chloride and diphenyl ether as raw materials, aluminum oxide as catalyst, 1,2-dichloroethane as solvent, under normal temperature, normal pressure, nitrogen atmosphere to generate PEAK. In-situ polymerization of PEAK was realized, and the material was TZP / PEAK composite matrix, and the mass ratio of TZP support to polyaryletherketone in the TZP / PEAK composite matrix was 4.6:1;

[0109] S3: The composite material was placed in an 80 ℃ condensation refluxing APTES / anhydrous ethanol (volume ratio 1:10) mixed solution for reaction for 12 h, and then washed with anhydrous ethanol and dried.

[0110] S4: 200 mg of Arg, 690 mg of EDC and 486 mg of HOBT were weighed and sequentially added into a DIPEA / DMF (volume ratio 1:25) mixed solution to obtain a mixed solution with an Arg concentration of 80 mg / ml, the composite material grafted with APTES was immersed in the mixed solution and placed under light stirring for 24 h, then washed with anhydrous DMF twice, RO water three times, and dried to obtain a composite crown restoration material.

[0111] A preparation method of a composite crown restoration material is provided, comprising the following contents:

[0112] S1: Nanometer zirconia particles are freeze-cast formed and sintered by a freeze casting technology (water is used as a solvent in the freeze casting slurry, and the content of nanometer zirconia is 55 wt%) to obtain a TZP support with sufficient strength (the content of nanometer zirconia is 55 wt%);

[0113] S2: In a 2L dry glass reaction kettle equipped with mechanical stirring and nitrogen inlet, the dried TZP support in step S1 is added, then PEAK is generated by using p-terephthaloyl chloride, m-terephthaloyl chloride and diphenyl ether as raw materials, aluminum oxide as catalyst, 1,2-dichloroethane as solvent, under normal temperature, normal pressure and nitrogen atmosphere. PEAK is in-situ polymerized to obtain a TZP / PEAK composite matrix, and the mass ratio of the TZP support to the polyaryletherketone in the TZP / PEAK composite matrix is 4.6:1;

[0114] S3: 200 mg of Arg is weighed and added into a mixed solution of DIPEA / DMF (volume ratio 1:25) to obtain a mixed solution with an Arg concentration of 80 mg / ml. The composite material synthesized in S2 is immersed in the mixed solution, and placed under light stirring for 24 h. After the reaction is completed, the composite material is washed twice with anhydrous DMF, three times with RO water, and dried to obtain a composite crown restoration material.

[0115] Test results

[0116] 1. The performance of the AMEM composite material prepared in Example 1 is detected, and zirconia and PEAK cut and prepared are used as controls. The test method and test results are as follows:

[0117] The detection method is as follows: after the sample is embedded with self-curing denture powder and water, the test surface is polished with a polishing machine, a polishing disc and polishing liquid until no obvious scratches are observed under a light microscope. After ultrasonic cleaning for 10 min and drying, the sample is ready for use. The loading, loading and unloading time of nanoindentation experiment are all 20 s, 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 regions of each sample are randomly selected for testing, and three samples are tested for each group. The test results (mean ± variance) of the elastic modulus and hardness of each group of materials are shown in Table 1:

[0118] Table 1 Test results of elastic modulus and hardness (mean ± variance)

[0119] Material Young's Modulus (GPa) Nano-hardness (GPa) TZP 178.37±6.40 13.61±1.25 AMEM 198.45±6.40 14.69±0.90 ZrO2 233.94±8.27 16.37±0.83 PEAK 5.89±0.06 0.29±0.02

[0120] 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:

[0121] After the material was mirror polished, 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 used as a reference. Figures 4-8 As shown, it was found that the wear amounts among the materials of 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 as the number of chewing cycles increases, 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, achieving the protective effect on enamel, and reducing the occurrence of fretting friction and wear. Therefore, compared with other commonly used 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, achieve the protective effect on enamel, and reduce the occurrence of fretting friction and wear.

[0122] 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:

[0123] Morphology and distribution of HGFs:

[0124] 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, and the cells were washed twice with PBS solution. Then, they were fixed with glutaraldehyde at 4 °C for​​​​​​​​4. The anti-S. 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 detected, and the detection method and detection results are as follows:

[0126] The morphology and distribution of Sm:

[0127] The morphology and distribution of bacteria on the material surface were observed by SEM. The material treatment and bacterial seed plate were the same as above, and the co-culture of S. mutans and the material was carried out. After 24 h of incubation in the incubator, the culture medium was removed, and the PBS solution was washed for 2 times, 4 ℃ glutaraldehyde fixation for 4 h, and the PBS solution was washed for 2 times, 5 min each time. Dehydration was carried out according to the gradient of anhydrous ethanol / double distilled water solution of 30%, 50%, 75%, 85%, 95%, and 100% volume fraction, 10 min for each gradient. After dehydration, the materials were dried at room temperature. The dried materials were adhered to the SEM sample table with conductive glue, the surface of the materials with bacteria was upward, and gold spraying was carried out in the vacuum sputtering machine for 3 min, and then the materials were placed in the SEM sample box, and the SEM was used to observe and record the images under high vacuum and 15 kV voltage. The results are shown in Figures 19-28 、 Figure 31 and Figure 32 The number of bacteria on the surface of the AMEM group was less, and there was no obvious biofilm formation. The number of bacteria on the surface of the composite materials in Comparative Example 2 and Comparative Example 3 was more than that in the AMEM group, and the Arg grafting was insufficient, which could not play a stable antibacterial effect.

[0128] The mechanical experiment proves that AMEM has good mechanical properties matched with dental enamel; the fretting friction and wear test proves that AMEM has a small friction coefficient and less enamel damage, which confirms that the material has good lubrication effect and enamel protection effect; the cell experiment proves that AMEM has good biocompatibility; the bacteria experiment proves that AMEM has good anti-cariogenic bacteria performance, and can resist cariogenic biofilm formation, and the comprehensive performance is the best.

[0129] In summary, AMEM not only has mechanical properties matched with dental enamel, reduces the damage of adjacent enamel in terms of mechanical matching and fretting friction and wear, but also has anti-cariogenic bacteria performance, adjusts the microenvironment of the material surface, plays a lubricating effect on the biofilm, prevents the demineralization and roughening of the enamel surface caused by the acid erosion of cariogenic bacteria, and prevents the adjacent enamel damage and the occurrence of food impaction.

[0130] Overall, the embodiment of the present application focuses on the biomechanical mechanism of food impaction occurring after fixed repair reconstruction, and innovatively attributes the initiation factor of food impaction after repair to the mechanical, biological and combined micro-wear and wear coupling interaction of the prosthetic material at the tooth contact. The present application breaks through the limitations of the previous single perspective research mode of dental wear research, which only focuses on the occlusal surface and ignores the mechanical role of biological membrane related research. The present application integrates the biological and mechanical perspectives, and constructs the coupling interaction mechanism of the biological matching and mechanical matching of the interproximal prosthetic material, and the synergistic effect of the two on the stability and loss of the tooth contact relationship. The present application innovatively synthesizes the organic and inorganic phase structure of natural enamel and has the function of regulating the microecology of the adjacent contact AMEM crown repair material.

[0131] In the embodiment of the present application, arginine is grafted to the surface of the composite material by introducing hydroxyl groups on the surface of TZP and PEAK and using APTES as an intermediate medium. Arginine is rich in carboxyl groups, and the stable and firm combination of arginine and the surface of the composite material is designed by using covalent bond. Arginine is grafted to the surface of the composite material to realize the special target surface modification of organic-inorganic materials. Different concentrations of arginine can be grafted on the special interface of organic-inorganic materials, and the function of regulating the microenvironment of the biological membrane is achieved. 80mg / ml is the best.

[0132] The embodiment of the present application compares the mechanical-biological matching advantage of the existing prosthetic material, and provides a cognitive basis for the research and development of new interproximal prosthetic materials and the tribological design of tooth contact in the future. The present application has scientificity and originality.

[0133] The biomimetic crown repair material prepared in the embodiment of the present application is adapted to the biological and mechanical properties of tooth enamel, can simultaneously realize the matching of biological and mechanical properties with tooth enamel, can regulate the microecological environment of the material surface, and finally realize the anti-micro-wear and wear effect, which is beneficial to reduce the loss of contact and prevent the occurrence of food impaction.

[0134] The above specific embodiments further illustrate the purpose, technical solutions and advantages of the present application. It should be understood that the above description is only a specific embodiment of the present application and does not limit the protection scope of the present application. Any modification, equivalent replacement, improvement, etc. made within the spirit and principles of the present application shall be included in the protection scope of the present application.

Claims

1. An enamel-like composite crown restorative material, characterized by, The composite material comprises a composite substrate, a net-like wrapping structure and arginine, the net-like wrapping structure is coated on the outside of the composite substrate, and the arginine is grafted on the net-like wrapping structure; the composite substrate comprises a TZP support and a polyaryletherketone; The net-like wrapping structure is formed by covalent bond between one side of siloxane hydrolyzed from gamma-aminopropyl triethoxysilane and the hydroxyl on the surface of the composite substrate, and the other side of the net-like wrapping structure is capable of condensation reaction with the carboxyl of arginine to complete grafting and coating; The preparation method of the enamel-like composite crown restoration material comprises the following steps: S1: nano zirconium oxide particles are frozen cast into a shape and sintered by a frozen casting technology to obtain a TZP support, and the proportion of TZP particles in the frozen casting slurry used is 50-60 wt%; S2: a TZP support is added, and a polyaryletherketone is generated by using the principle of Friedel-Crafts reaction to realize in-situ polymerization of the polyaryletherketone, thereby obtaining a TZP / PEAK composite substrate; S3: the TZP / PEAK composite substrate is immersed in a hydrogen peroxide solution and taken out after stirring, and then is sequentially cleaned and dried; then, UV light is irradiated to obtain hydroxyl modification on the surface of the TZP / PEAK composite substrate; S4: the TZP / PEAK composite substrate with completed hydroxyl modification is placed in a mixed solution of gamma-aminopropyl triethoxysilane and anhydrous ethanol to react, and then is cleaned with anhydrous ethanol and dried to obtain a composite material grafted with APTES; S5: arginine, 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide and 1-hydroxybenzotriazole are sequentially added into a mixed solution of diisopropylethylamine and dimethylformamide to obtain a mixed solution containing arginine, the composite material grafted with APTES is immersed in the mixed solution containing arginine to react, and then is sequentially cleaned and dried to obtain an AMEM composite material.

2. The enamel composite crown restoration material according to claim 1, characterized in that, The TZP support and the polyaryletherketone are arranged in an alternating layer shape, and the mass ratio of the TZP support to the polyaryletherketone in the composite substrate is 2.9-5.7:

1.

3. The enamel composite crown restoration material according to claim 2, characterized in that, The hydroxyl on the surface of the composite substrate comprises a hydroxyl on the TZP support and a hydroxyl on the surface of the polyaryletherketone; the hydroxyl on the TZP support is formed after the TZP support is treated by H2O2 functionalization; The hydroxyl on the surface of the polyaryletherketone is formed after the polyaryletherketone is irradiated by UV light.

4. A method for producing the enamel composite crown restorative material according to any one of claims 1 to 3, characterized by, The preparation method comprises the following steps: S1: nano zirconium oxide particles are frozen cast into a shape and sintered by a frozen casting technology to obtain a TZP support, and the proportion of TZP particles in the frozen casting slurry used is 50-60 wt%; S2: a TZP support is added, and a polyaryletherketone is generated by using the principle of Friedel-Crafts reaction to realize in-situ polymerization of the polyaryletherketone, thereby obtaining a TZP / PEAK composite substrate; S3: the TZP / PEAK composite substrate is immersed in a hydrogen peroxide solution and taken out after stirring, and then is sequentially cleaned and dried; then, UV light is irradiated to obtain hydroxyl modification on the surface of the TZP / PEAK composite substrate; S4: the TZP / PEAK composite matrix with the hydroxyl modification completed is placed in a mixed solution of γ-aminopropyl triethoxysilane and anhydrous ethanol for reaction, after the reaction, the composite material grafted with APTES is obtained by cleaning with anhydrous ethanol and drying; S5: arginine, 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide and 1-hydroxybenzotriazole are weighed and sequentially added into a mixed solution of diisopropyl ethylamine and dimethylformamide to obtain a mixed solution containing arginine, the composite material grafted with APTES is immersed in the mixed solution containing arginine for reaction, after the reaction, cleaning and drying are sequentially performed, and the AMEM composite material is obtained.

5. The method for preparing an enamel-like composite crown repair material according to claim 4, characterized in that, The polyaryletherketone generated in S2 by using the principle of Friedel-Crafts reaction includes the following steps: taking terephthaloyl chloride, isophthaloyl chloride and diphenyl ether as raw materials, taking aluminum trioxide as catalyst, and taking 1,2-dichloroethane as solvent to perform polymerization reaction.

6. The method for preparing an enamel-like composite crown repair material according to claim 4, characterized in that, In S3, the concentration of the hydrogen peroxide solution is 15-25%, the stirring temperature is 50-60℃, the stirring time is 4-8 hours, and the UV light irradiation time is 0.8-1.2 hours.

7. The method for preparing an enamel-like composite crown repair material according to claim 4, characterized in that, In S4, the volume ratio of γ-aminopropyl triethoxysilane to anhydrous ethanol is 1:8-12, the reaction temperature is 70-90℃, and the reaction time is 10-14 hours.

8. The method for preparing an enamel-like composite crown repair material according to claim 4, characterized in that, In S5, the concentration of arginine in the mixed solution containing arginine is 70-90mg / ml, the reaction time is 20-30 hours, the cleaning step includes cleaning with anhydrous DMF at least twice and cleaning with deionized water at least three times.

9. Use of the enamel composite crown restorative material according to any one of claims 1 to 3, characterized in that, The material is used for preparing a dental restoration, and the dental restoration includes at least one of a fixed / implanted dental crown, a dental bridge, and a dental veneer.

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