Silver-titanium bimetallic cluster-based antibacterial calcium silicate composite material, and preparation method and application thereof

Abstract

The application discloses a kind of silver titanium bimetallic cluster-based bacteriostatic calcium silicate composite material and its preparation method and application, by changing the temperature and time of muffle furnace calcination when preparing composite material, silver titanium composite material or calcium silicate composite material with different morphology structures can be obtained, wherein silver titanium composite material or calcium silicate composite material containing silver titanium obtained under specific conditions has significant bacteriostatic property, by adjusting the proportion of silver titanium composite material in calcium silicate, the bacteriostatic property of calcium silicate composite material is adjusted;The bacteriostatic calcium silicate composite material prepared by the application can be used as dental filling material, to play the bacteriostatic effect, to reduce the risk of bacterial infection.

Description

TECHNICAL FIELD

[0001] The present application relates to a silver-titanium bimetallic cluster and a bacteriostatic calcium silicate composite material based on the silver-titanium bimetallic cluster. The calcium silicate composite material prepared from the silver-titanium bimetallic cluster has excellent bacteriostatic performance and can be used as a dental filling material to reduce the risk of bacterial infection. BACKGROUND

[0002] Calcium silicate is a common dental filling material, which has many advantages. First, the calcium silicate filling can last for several years after proper treatment and maintenance, and has high durability. Second, the calcium silicate filling can be naturally combined with the tooth, avoiding gaps between the material and the tooth, and has good physical compatibility. In addition, the calcium silicate filling material has good biocompatibility with tooth tissue and almost no allergic reactions or discomfort, and has good biocompatibility. At the same time, the calcium silicate filling can prevent tooth erosion and caries, and has corrosion resistance. However, when using calcium silicate to fill teeth, there may be a problem of bacterial infection. Due to bleeding and wound enlargement during the operation, the tooth is infected internally, and the filling material cannot effectively kill bacteria. Therefore, how to minimize the risk of bacterial infection has become a key research direction.

[0003] Titanium dioxide is a commonly used medical material, which has good biocompatibility, excellent chemical stability, and does not cause any significant toxicity or allergic reactions. In medical applications, titanium dioxide can be used to make a variety of medical devices and equipment such as dental implants, artificial joints, and dental repair materials. Silver-titanium bimetallic cluster (Chen S, Chen Z N, Fang W H, et al. Ag10Ti28-Oxo Cluster Containing Single-Atom Silver Sites: Atomic Structure and Synergistic Electronic Properties [J]. Angewandte Chemie, 2019, 131(32): 11048-11051.) is a bimetallic cluster with titanium atoms as the main body and grafted with silver atoms, which has excellent bacteriostatic performance and can be used to prepare composite materials with bacteriostatic performance.

[0004] The present application combines silver-titanium bimetallic clusters with calcium silicate to obtain a calcium silicate composite material with excellent bacteriostatic performance. The bacteriostatic calcium silicate composite material described in the present application has a significant bacteriostatic effect and can inhibit the growth of bacteria when placed in a bacterial culture dish. SUMMARY

[0005] The application is prepared by compounding silver titanium bimetallic clusters with calcium silicate, and is a bacteriostatic calcium silicate composite material with significant bacteriostatic performance, which can be used as a dental filling material to reduce the risk of bacterial infection.

[0006] The technical scheme of the application is as follows:

[0007] A silver titanium bimetallic cluster is prepared by the following method:

[0008] Silver acetate and salicylic acid are dissolved in acetonitrile, and then acetic acid and titanium isopropoxide are added in sequence, and the reaction is carried out at 50-150 DEG C for 40-140 hours, and then cooled to room temperature to obtain a silver titanium bimetallic cluster solution;

[0009] The mass ratio of silver acetate to salicylic acid is 1:0.1-10, preferably 1:3.5-4.5;

[0010] The volume-mass ratio of acetonitrile to silver acetate is 10-100:1, mL / g, preferably 80:1, mL / g;

[0011] The volume-mass ratio of acetic acid to silver acetate is 10-100:1, mL / g, preferably 80:1, mL / g;

[0012] The volume-mass ratio of titanium isopropoxide to silver acetate is 1-10:1, mL / g, preferably 2:1, mL / g;

[0013] The preferred reaction temperature is 70 DEG C, and the reaction time is 48 hours.

[0014] A silver titanium composite material based on silver titanium bimetallic clusters is prepared by the following method:

[0015] The silver titanium bimetallic cluster solution prepared above is filtered to obtain a precipitate, which is calcined in a muffle furnace at 50-800 DEG C for 0.5-72 hours to obtain a silver titanium composite material;

[0016] The preferred calcination temperature is 50-200 DEG C, and the calcination time is 24 hours.

[0017] A bacteriostatic calcium silicate composite material based on silver titanium bimetallic clusters is prepared by the following method:

[0018] Silver titanium bimetallic clusters are prepared by the following method:

[0019] The mass ratio of calcium silicate to silver acetate, the raw material of silver titanium bimetallic clusters, is 0.1-1000:1;

[0020] The preferred calcination temperature is 50-200 DEG C, and the calcination time is 24 hours.

[0021] In the present application, the precipitate obtained by filtering the silver-titanium bimetallic cluster solution is calcined at different temperatures in a muffle furnace for different time to obtain silver-titanium composite materials with different morphological structures. In order to obtain silver-titanium composite materials or calcium silicate composite materials with antibacterial properties, the calcination temperature of the muffle furnace cannot be too high to prevent the oxidation of silver in the silver-titanium bimetallic cluster into silver single element, thereby reducing the antibacterial properties. The calcination temperature in the muffle furnace is preferably 50-200°C, and the calcination time is preferably 24 hours. In addition, by controlling the ratio of calcium silicate to silver acetate, calcium silicate composite materials with different proportions of silver-titanium content can be obtained to adjust the antibacterial properties of the calcium silicate composite materials.

[0022] The antibacterial calcium silicate composite material prepared in the present application can be used as a dental filling material to achieve antibacterial effect and reduce the risk of bacterial infection.

[0023] The present application has the following beneficial effects:

[0024] A silver-titanium composite material or an antibacterial calcium silicate composite material prepared based on silver-titanium bimetallic clusters is provided. By changing the temperature and time of calcination in a muffle furnace during the preparation of the composite material, silver-titanium composite materials or calcium silicate composite materials with different morphological structures can be obtained. The silver-titanium composite material or the calcium silicate composite material containing silver-titanium obtained under certain conditions has significant antibacterial properties, and by adjusting the proportion of silver-titanium composite material in the calcium silicate, the antibacterial properties of the calcium silicate composite material can be adjusted. BRIEF DESCRIPTION OF DRAWINGS

[0025] Figure 1 The SEM image of the silver-titanium composite material calcined at 800°C in a muffle furnace for 24 hours shows a large number of nano-porous structures (pore size is about several hundred nanometers), which has a large specific surface area, and the material has no antibacterial properties.

[0026] Figure 2 The SEM image of the silver-titanium composite material calcined at 150°C in a muffle furnace for 24 hours shows that the material is mainly composed of small particles with a size of several hundred nanometers, and the material has obvious antibacterial properties.

[0027] Figure 3 The SEM image of pure calcium silicate calcined at 150°C in a muffle furnace for 24 hours shows that the pure calcium silicate is in the form of small blocks with a size of several microns, and the material has no antibacterial properties.

[0028] Figure 4 The SEM image of the calcium silicate composite material containing silver-titanium calcined at 150°C in a muffle furnace for 24 hours shows that there are obvious nano-silver-titanium particles attached to the surface of the calcium silicate, and the material has obvious antibacterial properties.

[0029] Figure 5EDS pattern of silver-titanium composite material calcined at 150°C for 24 hours in a muffle furnace, in which the silver content is about 2.3%, and the titanium content is about 4.9%.

[0030] Figure 6 EDS pattern of silver-titanium-containing calcium silicate composite material calcined at 150°C for 24 hours in a muffle furnace, in which the silver content is about 0.2%, the titanium content is about 1.2%, the calcium content is about 1.7%, and the silicon content is about 1.7%.

[0031] Figure 7 Infrared spectrum of silver-titanium composite material calcined at 150°C for 24 hours in a muffle furnace, which is highly similar to the infrared spectrum of salicylic acid, indicating that the silver-titanium bimetallic cluster [AgTi(SC)2(HSC)(CH3CN)] still retains the structure of salicylic acid during the preparation of the silver-titanium composite material. The characteristic peaks of 400-500 cm -1 in the infrared spectrum correspond to Ag-O bonds, and the characteristic peaks of 600-800 cm -1 correspond to Ti-O bonds.

[0032] Figure 8 The figure is the antibacterial test result of silver-titanium composite material and silver-titanium-containing calcium silicate composite material, using Staphylococcus aureus as the bacterial strain and culturing for 7 days. The silver-titanium composite material calcined at 150°C for 24 hours and the silver-titanium-containing calcium silicate composite material calcined at 150°C for 24 hours have significant antibacterial performance, and no bacteria are found to grow compared to the blank control of 116 bacteria. The silver-titanium composite material calcined at 800°C for 24 hours has no antibacterial performance, and the number of bacteria is almost the same as the blank control.

[0033] Figure 9 The figure is a photo of the orange crystals [AgTi(SC)2(HSC)(CH3CN)] obtained in Example 3. DETAILED DESCRIPTION

[0034] The present application will be further described below through specific examples, but the scope of protection of the present application is not limited thereto.

[0035] Example 1

[0036] The preparation process of the silver-titanium bimetallic cluster solution is as follows:

[0037] 0.15g of silver acetate and 0.60g of salicylic acid were dissolved in 12ml of acetonitrile, then 12ml of acetic acid and 0.3ml of titanium isopropoxide were added in sequence, and the reaction was carried out at 70°C for 48h, and then cooled to room temperature to obtain the silver-titanium bimetallic cluster solution.

[0038] Example 2

[0039] The preparation process of the silver-titanium bimetallic cluster solution is as follows:

[0040] Dissolve 0.5 g silver acetate and 1.0 g salicylic acid in 30 ml acetonitrile, then add 30 ml acetic acid and 2.0 ml titanium isopropoxide in sequence, and react at 100 °C for 24 h, and then cool to room temperature to obtain a silver-titanium bimetallic cluster solution.

[0041] Example 3

[0042] Put the silver-titanium bimetallic cluster solution obtained in Example 1 in a constant humidity and temperature oven at 25 °C and 40% humidity for 20 days to obtain orange crystals, and the structure of the crystals is [AgTi(SC)2(HSC)(CH3CN)] (HSC is salicylic acid), which is specifically described in Figure 9 .

[0043] Example 4

[0044] Filter the silver-titanium bimetallic cluster solution obtained in Example 1 to obtain a precipitate, and then calcine the precipitate in a muffle furnace at 800 °C for 24 h to obtain a silver-titanium composite material, which has a large number of nano-porous structures (with a pore size of about several hundred nanometers) and a large specific surface area, but almost no antibacterial performance (as an example, the growth of Staphylococcus aureus and the blank control are basically the same after 7 days of culture). The microstructure is specifically described in Figure 1 , and the antibacterial performance is specifically described in Figure 8 .

[0045] Example 5

[0046] Filter the silver-titanium bimetallic cluster solution obtained in Example 1 to obtain a precipitate, and then calcine the precipitate in a muffle furnace at 150 °C for 24 h to obtain a silver-titanium composite material, which is mainly composed of small-sized particles with a size of several hundred nanometers and has obvious antibacterial performance (as an example, no bacteria grow after 7 days of culture of Staphylococcus aureus). The microstructure is specifically described in Figure 2 , the elemental composition is specifically described in Figure 5 , the infrared spectrum is specifically described in Figure 7 , and the antibacterial performance is specifically described in Figure 8 .

[0047] Example 6

[0048] Add 3 g calcium silicate to the silver-titanium bimetallic cluster solution obtained in Example 1, shake vigorously, filter to obtain a precipitate, and then calcine the precipitate in a muffle furnace at 150 °C for 24 h to obtain a silver-titanium-containing calcium silicate composite material, which has obvious nano-silver-titanium particles attached to the surface of the calcium silicate and has obvious antibacterial performance (as an example, no bacteria grow after 7 days of culture of Staphylococcus aureus). The microstructure is specifically described in Figure 4 , the elemental composition is specifically described in Figure 6 , and the antibacterial performance is specifically described inFigure 8 。

Claims

1. A bacteriostatic calcium silicate composite material, characterized by, The preparation method is as follows: The silver-titanium bimetallic cluster solution is prepared by the following method: The silver-titanium bimetallic cluster solution is prepared by the following method: The silver-titanium bimetallic cluster solution is prepared by the following method:

2. The bacteriostatic calcium silicate composite material according to claim 1, wherein, The silver-titanium bimetallic cluster solution is prepared by the following method:

3. The bacteriostatic calcium silicate composite material of claim 1, wherein, The silver-titanium bimetallic cluster solution is prepared by the following method: The silver-titanium bimetallic cluster solution is prepared by the following method: The silver-titanium bimetallic cluster solution is prepared by the following method: The silver-titanium bimetallic cluster solution is prepared by the following method: The silver-titanium bimetallic cluster solution is prepared by the following method: The silver-titanium bimetallic cluster solution is prepared by the following method: The silver-titanium bimetallic cluster solution is prepared by the following method: The silver-titanium bimetallic cluster solution is prepared by the following method: The silver-titanium bimetallic cluster solution is prepared by the following method: The silver-titanium bimetallic cluster solution is prepared by the following method: The silver-titanium bimetallic cluster solution is prepared by the following method: The silver-titanium bimetallic cluster solution is prepared by the following method: The silver-titanium bimetallic cluster solution is prepared by the following method: The silver-titanium bimetallic cluster solution is prepared by the following method: The silver-titanium bimetallic cluster solution is prepared by the following method: The silver-titanium bimetallic cluster solution is prepared by the following method: The silver-titanium bimetallic cluster solution is prepared by the following method: The silver-titanium bimetallic cluster solution is prepared by the following method: The silver-titanium bimetallic cluster solution is prepared by the following method: The silver-titanium bimetallic cluster solution is prepared by the following method: The silver-titanium bimetallic cluster solution is prepared by the following method: The silver-titanium bimetallic cluster solution is prepared by the following method: The silver-titanium bimetallic cluster solution is prepared by the following method: The silver-titanium bimetallic cluster solution is prepared by the following method: The silver-titanium bimetallic cluster solution is prepared by the following method: The silver-titanium bimetallic cluster solution is prepared by the following method: The silver-titanium bimetallic cluster solution is prepared by the following method: The silver-titanium bimetallic cluster solution is prepared by the following method: The silver-titanium bimetallic cluster solution is prepared by the following method: The silver-titanium bimetallic cluster solution is prepared by the following method: The silver-titanium bimetallic cluster solution is prepared by the following method: The silver-titanium bimetallic cluster solution is prepared by the following method: The

Images