Zinc oxide clove oil cement composite material with enhanced antibacterial and compressive properties and preparation method thereof

Abstract

The invention belongs to the technical field of novel functional and structural materials, and particularly discloses a zinc oxide clove oil cement composite material with enhanced antibacterial and compressive properties and a preparation method thereof, the composite material is prepared by taking ZOE as a main material of the composite material and blending PZnO (at) Cur, ZnONWs and ZOE, and the purpose of enhancing the antibacterial and compressive properties of the raw material is achieved. The PZnO in the composite material can be slowly degraded in a weak acid environment in which bacteria breed, and the loaded Cur is released, so that the pH response controlled release effect of the medicine is realized, the antibacterial effect is improved, the bioavailability of the medicine is improved, and the potential toxicity is reduced. Furthermore, ZnONWs is used as a reinforcing phase to improve the compressive strength of the main body material. By optimizing the proportion parameter of each component, the zinc oxide clove oil cement composite material with optimal antibacterial and compressive properties is finally obtained. The method is simple in preparation process, low in cost, safe and controllable, and has potential application prospects in the field of novel functional and structural materials.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of new functional and structural materials, and relates to preparation of a temporary sealing material, zinc oxide eugenol cement, for treatment of oral diseases, in particular to a zinc oxide eugenol cement composite material with enhanced antibacterial and compression resistance and a preparation method thereof. BACKGROUND

[0002] Temporary sealing materials are an important class of materials widely used in clinical work of stomatology, and are mainly used in the treatment of common oral diseases such as caries, pulp and periapical diseases, and part of periodontal diseases. The core role is to temporarily seal the treatment area during the gap period of pulp devitalization, root canal treatment, vital pulp amputation and root apex induction shaping, etc. treatment stage, which not only provides a relatively closed action environment for drugs, but also creates favorable conditions for subsequent treatment. The temporary sealing materials commonly used in the clinic at present mainly include zinc oxide, glass ionomer, cement and resin, among which zinc oxide eugenol cement (ZOE) is one of the most widely used short-term temporary sealing materials in China. ZOE is prepared by mixing zinc oxide powder and eugenol solution in a specific ratio: zinc oxide has antiseptic and astringent effects and can protect the wound; eugenol exerts antiseptic and analgesic effects. The material has the following advantages: good biocompatibility and pulp soothing effect; excellent sealing performance in a humid oral environment due to its rapid curing characteristics when it comes into contact with water; simple operation and low cost; long available time after preparation, and convenient clinical operation and removal. The antibacterial effect of ZOE mainly depends on the eugenol component, which has analgesic and antibacterial effects and can inhibit the growth of various oral bacteria such as Streptococcus mutans and Porphyromonas gingivalis. However, ZOE is easily dissolved in water and saliva, and the release of eugenol may weaken its long-term antibacterial effect, and the antibacterial effect of eugenol alone is limited. Therefore, it is necessary to develop new ZOE composite materials to balance its long-term antibacterial effect and biocompatibility.

[0003] The compressive strength of the temporary sealing material is a key indicator affecting the clinical efficacy, which determines the deformation and fragmentation risk of the material under the chewing pressure. Once the material is damaged due to insufficient compression, its edge sealing will completely fail (Zhao Shouliang, Zhang Shaofeng, Li Yun, et al. Stress analysis of dental tissues after amalgam filling. 2003, 5: 474-476). However, the compressive strength of traditional ZOE is only 25-35 MPa, and the enhanced type is 45-55 MPa. The solubility (24-hour dissolution rate 1.5%) will further weaken the mechanical properties when exposed to the humid environment of the oral cavity for a long time, and it is difficult to withstand the constant chewing force (usually 1.5-3 MPa) (Jin Yifu, Feng Shanshan, Chen Huan, et al. Research progress of finite element analysis in the application of oral adhesive cement. Modern Oral Medicine Journal, 2023, 37(02): 105-109). Therefore, improving the antibacterial performance and compressive strength of the temporary sealing material (especially ZOE) is of great significance to ensure the clinical treatment effect. The current research focuses on optimizing the material raw material formula to solve the limitations in mechanical strength and stability of maintaining antibacterial treatment effect. SUMMARY

[0004] In view of the shortcomings of the prior art, the purpose of the present application is to provide a zinc oxide eugenol cement composite material with enhanced antibacterial and compressive properties, which can enhance the antibacterial performance and compressive strength of the temporary sealing material ZOE in the environment of oral infection and inflammation; another purpose of the present application is to provide a preparation method of the composite material.

[0005] The present application is realized by the following technical solutions: A zinc oxide eugenol cement composite material with enhanced antibacterial and compressive properties, the composite material takes ZOE as the main material of the composite material, and PZnO@Cur and ZnONWs are respectively used as composite phases for enhancing the antibacterial and compressive properties of the composite material, and PZnO@Cur, ZnONWs and ZOE are blended to obtain the composite material.

[0006] Further improved schemes of the present application are: A preparation method of a zinc oxide eugenol cement composite material with enhanced antibacterial and compressive properties, comprising the following steps: (1) Zn(NO3)2·6H2O and polyvinylpyrrolidone are dissolved into an aqueous urea solution, stirred, and then subjected to high-pressure reaction, and after reaction, centrifugation, deionized water washing and drying; then the product is transferred to a muffle furnace for high-temperature calcination for a period of time to obtain a porous zinc oxide material, denoted as PZnO; (2) PZnO is added to a curcumin solution, stirred in the dark for a period of time, and then washed with methanol and water in sequence after centrifugation, and vacuum dried to obtain a PZnO sample loaded with curcumin, denoted as PZnO@Cur; (3) Zn(CH3COO)2·2H2O, NaOH and sodium dodecyl sulfate are dissolved in PEG400 ethanol solution, after stirring, high pressure reaction is carried out, after reaction, the product is centrifuged, washed with deionized water and ethanol, dried, and annealed at high temperature for a period of time, to obtain ZnO nanowires, recorded as ZnONWs; (4) PZnO@Cur, ZnONWs, ZnO powder and clove oil liquid are uniformly mixed and stirred, and after standing for a period of time, PZnO@Cur / ZnONWs / ZOE composite material is obtained.

[0007] Further improved schemes of the present application are: In step (1), the amount ratio of Zn(NO3)2·6H2O, polyvinylpyrrolidone and urea aqueous solution is 1-2g:1-3g:150-200mL; the concentration of the urea aqueous solution is 40-60mmol·L -1 , and the stirring time is 1-3h.

[0008] Further, in step (1), the temperature of the high pressure reaction is 100-130℃, and the time is 12-24h; the temperature of the drying is 60-80℃, and the time is 12-24h.

[0009] Further, in step (1), the temperature of the high temperature calcination is 300-400℃, and the time is 3-4h.

[0010] Further, in step (2), the amount ratio of PZnO and curcumin solution is 1-1.5g:250-500mL; the concentration of the curcumin solution is 50-100ppm, and the solvent is methanol; and the light-shielded stirring time is 3-5h.

[0011] Further, in step (3), the amount ratio of Zn(CH3COO)2·2H2O, NaOH, sodium dodecyl sulfate and PEG400 ethanol solution is 2-3g:10-15g:0.5-1g:50-200mL; the volume concentration of the PEG400 ethanol solution is 40-50%; and the stirring time is 1-2h.

[0012] Further, in step (3), the temperature of the high pressure reaction is 120-150℃, and the time is 12-24h.

[0013] Further, in step (3), the temperature of the annealing is 400-500℃, and the time is 3-4h.

[0014] Further, in step (4), the PZnO@Cur, ZnONWs, ZnO powder and clove oil liquid are used in a ratio of 0.5-1g:0.5-1g:3.5-5g:1mL; and the molding time is 1-2h.

[0015] Compared with the prior art, the present application has the following advantages: The PZnO@Cur and ZnONWs are blended with ZOE to prepare a PZnO@Cur / ZnONWs / ZOE composite material, so as to enhance the antibacterial and compression properties of the raw materials. The porous structure of the PZnO in the composite material provides sufficient adsorption sites for the electrostatic adsorption of curcumin. The PZnO prepared in the present application has a rich irregular pore structure, and the pore size is about 500 nm; the ZnONWs prepared has a diameter size of about 2 μm. The PZnO will slowly degrade in the weakly acidic environment where bacteria breed, so as to release the curcumin loaded therein, realize the controlled release of the drug, improve the bioavailability of the drug, and reduce the potential toxicity; the zinc oxide nanowires (ZnONWs) as the reinforcing phase can improve the compression strength of the matrix material, and finally realize the synergistic enhancement effect of the antibacterial and compression properties. BRIEF DESCRIPTION OF DRAWINGS

[0016] Figure 1 A physical map of the PZnO@Cur / ZnONWs / ZOE composite material prepared in Example 1; Figure 2 A scanning electron microscope map of the PZnO material prepared in Example 1; Figure 3 A scanning electron microscope map of the ZnONWs material prepared in Example 1; Figure 4 A pH response Cur release fold line graph of the PZnO@Cur / ZnONWs / ZOE composite material. DETAILED DESCRIPTION

[0017] The present application will be described in detail below in combination with specific embodiments.

[0018] Example 1: The PZnO@Cur / ZnONWs / ZOE composite material provided in the present embodiment takes ZOE as the matrix material in the composite material, and the PZnO@Cur and ZnONWs are blended with ZOE, and the specific preparation method is as follows: (1) 1.2g of Zn(NO3)2·6H2O and 2g of polyvinylpyrrolidone are dissolved into 160mL of 50mmol·L -1in 100 mL of 50% (V / V) PEG400 ethanol solution, stirred for 1 h, and then transferred into a high-pressure reactor and heated at 130 °C for 12 h. The obtained product was washed with water for 3 times and dried at 70 °C for 12 h. Finally, the product was calcined in a muffle furnace at 350 °C for 3 h to obtain porous ZnO (PZnO) nanosheets; (2) 1 g of PZnO was added into 250 mL of curcumin methanol solution (50 ppm) and stirred in the dark for 3 h. After centrifugation, the product was washed with water for 3 times and dried in vacuum to obtain a curcumin-loaded PZnO sample (PZnO@Cur); (3) 2.2 g of Zn(CH3COO)2·2H2O, 12.5 g of NaOH and 0.5 g of sodium dodecyl sulfate were dissolved in 100 mL of 50% (V / V) PEG400 ethanol solution, stirred for 1 h, and then transferred into a high-pressure reactor and heated at 140 °C for 16 h. The obtained product was washed with deionized water and ethanol, respectively, dried at 60 °C for 24 h, and annealed at 500 °C for 3 h to obtain ZnO nanowires (ZnONWs); (4) 0.5 g of PZnO@Cur, 0.5 g of ZnONWs, 3.5 g of ZnO powder and 1 mL of clove oil were mixed uniformly, and then PZnO@Cur / ZnONWs / ZOE composite material was obtained after standing for 1 h. The actual picture is shown in Figure 1 .

[0019] The micro-morphology of PZnO prepared in Example 1 was characterized, and the results are shown in Figure 2 . The nanomaterial has a rich porous structure, and the pore size is about 500 nm. The rich porous structure of the PZnO material can increase its specific surface area, which plays an important role in promoting the electrostatic adsorption of curcumin.

[0020] The micro-morphology of ZnONWs prepared in Example 1 was characterized, and the results are shown in Figure 3 . The nanomaterial has a typical fibrous structure, and the fiber diameter size is about 2 µm. The fibrous structure of the ZnONWs material has a positive effect on enhancing the compressive strength of the composite material.

[0021] Example 2

[0022] The difference between this example and Example 1 is that in step (4), the amounts of PZnO@Cur, ZnONWs, ZnO powder and clove oil liquid are 0.3 g, 0.3 g, 3.9 g and 1 mL, respectively, and other operations are substantially the same as those of Example 1, which will not be repeated here.

[0023] Example 3

[0024] The difference between this embodiment and embodiment 1 is that in step (4), the amounts of PZnO@Cur, ZnONWs, ZnO powder and clove oil liquid are 0.7g, 0.7g, 3.1g and 1mL, respectively. Other operations are roughly the same as in embodiment 1, and will not be repeated here.

[0025] Comparative Example 1: Preparation of ZOE matrix material (1) Mix 3.5g of ZnO powder and 1mL of clove oil liquid evenly, and follow the same steps (4) as in Example 1 to obtain ZOE sample.

[0026] Comparative Example 2: Preparation of PZnO@Cur / ZOE composite materials (1) The PZnO@Cur composite material was prepared using the same method as in Example 1; (2) Mix 0.5g of PZnO@Cur, 3.5g of ZnO powder and 1mL of clove oil liquid, stir evenly, and let stand for 1h to obtain PZnO@Cur / ZOE sample.

[0027] Comparative Example 3: The ZnONWs / ZOE composite material prepared in this study (1) Preparation of ZnONWs nanomaterials, the method is the same as in Example 1; (2) Mix 0.5g of ZnONWs, 3.5g of ZnO powder and 1mL of clove oil liquid, stir evenly, and let stand for 1h to obtain ZnONWs@Cur / ZOE sample.

[0028] Example 4: Performance testing of the materials prepared in the examples and comparative examples. 1. pH-responsive Cur release: To assess the pH-responsive Cur release performance of Examples 1, 2, 3, Comparative Examples 1, 2, and 3, the samples were immersed in aqueous media at different pH values ​​(5.8, 7.4, and 8.0). Supernatants were collected at specific time points (0, 2, 5, 10, 20, 30, 40, 50, 60, 70, 80, and 90 minutes), and measurements were taken using a UV-Vis spectrophotometer. The amount of Cur released was evaluated based on the absorbance at λ = 430 nm.

[0029] like Figure 4 As shown, in Examples 1, 2, 3 and Comparative Example 2, the amount of Cur released gradually increased with increasing ZnONWs@Cur doping, while in Comparative Examples 1 and 2, there was no Cur release due to the absence of ZnONWs@Cur doping. Importantly, the amount of Cur released from the sample groups increased significantly with decreasing pH, exhibiting a clear pH-responsive Cur release performance.

[0030] 2. Compression resistance test The compressive strength of each sample material was tested using a mechanical universal material testing machine. As shown in Table 1, the compressive strength of Examples 1, 3 and 2 gradually decreased, i.e. when the amount ratio of PZnO@Cur, ZnONWs, ZnO powder and clove oil liquid was 0.5 g:0.5 g:3.5 g:1 mL, the compressive strength of the composite material was optimal.

[0031] Table 1 Compressive strength test results of materials prepared in Examples and Comparative Examples Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Compressive strength (MPa) 52 40 43 33 35 48 3. Antibacterial experiment: Escherichia coli and Staphylococcus aureus were selected as experimental bacteria for the antibacterial experiment. The recovered bacteria were placed in a liquid culture medium and shaken overnight in a 37°C constant temperature shaker. The samples of Example 1, Example 2, Example 3, Comparative Example 1, Comparative Example 2 and Comparative Example 3 were placed in a 12-well plate, and 100 μL of bacterial solution was added to the surface of each sample. After 24 hours, 1 mL of PBS solution was added to each sample, which was then ultrasonically treated, and 50 μL of bacterial solution was taken and plated, and then observed for the number of bacterial colonies after being placed in a 37°C constant temperature shaker overnight.

[0032] Table 2 Bacterial survival rate results of materials prepared in Examples and Comparative Examples Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Escherichia coli 8.4 20.2 4.1 28.1 12.0 29.1 Staphylococcus aureus 9.3 22.1 5.0 26.5 10.9 26.8 The plate colony count data of the in vitro antibacterial experiment is shown in Table 2 above. The results show that Examples 1, 2, 3, Comparative Example 1, Comparative Example 2 and Comparative Example 3 all exhibit certain antibacterial effects on Escherichia coli and Staphylococcus aureus. Among them, the antibacterial efficiency of Example 3 and Example 1 is more obvious.

[0033] The above description of the embodiments is only to illustrate the technical concept and characteristics of the present application, and the purpose is to enable those skilled in the art to understand the content of the present application and implement it. Those skilled in the art can obviously easily make various modifications to these embodiments, and apply the general principles described herein to other embodiments without having to go through creative labor, therefore, the above embodiments cannot limit the protection scope of the present application. Any improvements and modifications made by those skilled in the art based on the disclosure of the present application without departing from the scope of the present application shall be covered within the protection scope of the present application.

Claims

1. A zinc oxide eugenol cement composite material with enhanced antibacterial and compressive strength properties, characterized in that, The composite material uses ZOE as the main material and PZnO@Cur and ZnONWs as composite phases that enhance antibacterial and compressive properties, respectively, and is obtained by blending PZnO@Cur, ZnONWs and ZOE.

2. The method for preparing a zinc oxide eugenol cement composite material with enhanced antibacterial and compressive strength properties as described in claim 1, characterized in that, Includes the following steps: (1) Dissolve Zn(NO3)2·6H2O and polyvinylpyrrolidone in urea aqueous solution, stir, and then carry out high pressure reaction. After the reaction, centrifuge, wash with deionized water, and dry. The product is then transferred to a muffle furnace and calcined at high temperature for a period of time to obtain porous zinc oxide material, denoted as PZnO; (2) PZnO was added to curcumin solution, stirred in the dark for a period of time, centrifuged, washed with methanol and water in sequence, and vacuum dried to obtain PZnO sample loaded with curcumin, denoted as PZnO@Cur; (3) Dissolve Zn(CH3COO)2·2H2O, NaOH and sodium dodecyl sulfate in PEG400 ethanol solution, stir, and carry out high pressure reaction. After the reaction, the product is centrifuged, washed with deionized water and ethanol, dried, and annealed at high temperature for a period of time to obtain ZnO nanowires, denoted as ZnONWs. (4) PZnO@Cur, ZnONWs, ZnO powder and clove oil liquid are mixed and stirred evenly, and after standing for a period of time to form, PZnO@Cur / ZnONWs / ZOE composite material is obtained.

3. The preparation method according to claim 2, characterized in that: In step (1), the ratio of Zn(NO3)2·6H2O, polyvinylpyrrolidone, and urea aqueous solution is 1-2g:1-3g:150-200mL; the concentration of the urea aqueous solution is 40-60mmol·L. -1 The stirring time is 1-3 hours.

4. The preparation method according to claim 2, characterized in that: In step (1), the high-pressure reaction is carried out at a temperature of 100-130℃ for 12-24 hours; the drying is carried out at a temperature of 60-80℃ for 12-24 hours.

5. The preparation method according to claim 2, characterized in that: In step (1), the high-temperature calcination temperature is 300-400℃ and the time is 3-4h.

6. The preparation method according to claim 2, characterized in that: In step (2), the ratio of PZnO to curcumin solution is 1-1.5g:250-500mL; the concentration of curcumin solution is 50-100ppm, and the solvent is methanol; the stirring time in the dark is 3-5h.

7. The preparation method according to claim 2, characterized in that: In step (3), the ratio of Zn(CH3COO)2·2H2O, NaOH, sodium dodecyl sulfate and PEG400 ethanol solution is 2-3g:10-15g:0.5-1g:50-200mL; the volume concentration of PEG400 ethanol solution is 40-50%; and the stirring time is 1-2h.

8. The preparation method according to claim 2, characterized in that: In step (3), the high-pressure reaction is carried out at a temperature of 120-150°C for 12-24 hours.

9. The preparation method according to claim 2, characterized in that: In step (3), the annealing temperature is 400-500℃ and the time is 3-4h.

10. The preparation method according to claim 2, characterized in that: In step (4), the ratio of the amount of PZnO@Cur, ZnONWs, ZnO powder and clove oil liquid is 0.5-1g:0.5-1g:3.5-5g:1mL; the molding time is 1-2h.

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