Preparation method of toothbrush with PPy / PBT conductive antibacterial bristles containing PPy coating

Abstract

The invention provides a preparation method of a toothbrush with PPy / PBT conductive antibacterial bristles. The preparation method comprises a step of preparing a pyrrole solution and a ferric chloride solution and a step of carrying out in-situ oxidative polymerization on pyrrole monomers on the surfaces of the bristles. The prepared toothbrush with the PPy / PBT conductive antibacterial bristles can resist bacteria while being electrified, has the advantages of being excellent in conductivity, low in toxicity and side effect and electrified antibacterial property, suitable for people of all ages and the like, not only can effectively solve the problem of bacterium breeding of the bristles, but also can kill bacteria originally existing in the oral cavity, better protects teeth, and is suitable for popularization and application. And the toothpaste is friendly to children, old people and people with oral health problems.

Description

Technical Field

[0001] The present invention relates to the field of biomedical antibacterial materials, and more specifically, to a method for preparing a toothbrush with PPy / PBT conductive antibacterial bristles containing a PPy coating. Background Art

[0002] As people's quality of life improves, more and more people are paying attention to oral health issues. Toothbrushes, as an indispensable tool for daily oral cleaning, can effectively prevent various oral diseases such as dental plaque, caries, periodontitis, etc. While developing different functions of toothbrushes, the antibacterial properties of the bristles need to be paid attention to.

[0003] In the process of daily use of toothbrushes, bacteria from the mouth and the air are easily contaminated on the bristles, and the environment where the toothbrushes are placed is usually relatively humid, which promotes the growth of bacteria on the bristles. These bacteria enter the mouth and the human body through the bristles during brushing, causing oral problems. At present, technicians have paid attention to the problem of antibacterial properties of bristles and have developed a preparation process for adding metal ions, such as silver ions, copper ions, etc., and metal salts, such as zinc sulfate, zinc chloride, etc., to toothbrush bristles. However, these antibacterial substances themselves have biological toxicity and may be absorbed by the human body during use. Due to the problems of biological toxicity and single function of current antibacterial materials, there is an urgent need to develop antibacterial materials with new functions for use in the preparation of antibacterial toothbrushes to address such problems.

[0004] At the same time, the discovery and confirmation of "antibacterial properties after charging" in recent years has provided a new method to give medical materials antibacterial properties. For example: in addition to traditional physical and chemical surface modification methods, people can make the titanium dioxide surface of orthopedic implant materials antibacterial through simple charging, thereby reducing the risk of postoperative infection and complications. This new method of "antibacterial properties after charging" can also avoid the side effects of traditional physical and chemical modification methods, promote the adhesion and growth of osteoblasts on the surface of implants, and is very beneficial for post-fracture repair treatment. At the same time, the revelation of the "antibacterial properties after charging" phenomenon has also given people a new understanding of the interaction between electricity, materials and organisms, and it is expected that more electrical modification schemes for materials and more uses will be designed based on this. Summary of the invention

[0005] In view of the above-mentioned technical problems in the prior art, the present invention provides a method for preparing a toothbrush with PPy / PBT conductive antibacterial bristles containing a PPy coating. The method for preparing a toothbrush with PPy / PBT conductive antibacterial bristles containing a PPy coating is intended to solve the technical problems in the prior art that the antibacterial materials have biological toxicity and a single function.

[0006] The present invention also provides a method for preparing the above-mentioned toothbrush with PPy / PBT conductive antibacterial bristles containing a PPy coating, comprising the following steps:

[0007] (1) A step of separately preparing a pyrrole solution and a ferric chloride solution by dissolving pyrrole monomer and non-hydrated ferric chloride in water.

[0008] (2) A step of oxidative polymerization of pyrrole monomers on the bristle surface is performed by chemical deposition method, wherein the pyrrole monomers are oxidized by trivalent iron ions.

[0009] Further, in step 1), the toothbrush is ultrasonically cleaned in ethanol for 30 minutes to completely remove residual impurities. 1.2 g of pyrrole monomer (Py) is evenly dripped onto the bristles of the PBT toothbrush, and then the brush head is immersed in 100 mL of deionized water to form a pyrrole solution, labeled solution A. 8.0 g of non-hydrated ferric chloride is added to 100 mL of deionized water to form a ferric chloride solution, labeled solution B, and one end of the toothbrush with bristles is immersed in solution A, and the entire system is fully stirred in an ice bath. The two solutions are fully cooled in an ice bath;

[0010] 8. Further, in step 2), solution B is slowly (about 1 drop / 2 seconds) added to the bristles until all are added. The end of the toothbrush with bristles is immersed in solution A. The in-situ oxidative polymerization of pyrrole monomer on the bristle surface lasts for 3 hours, and the reaction temperature is maintained at 0°C. During the reaction, it is clearly observed that the color of the bristles changes to black, indicating that PPy is formed on the bristle surface. The prepared bristles are washed several times with deionized water and ethanol, and then dried in an oven to obtain PPy / PBT conductive bristles;

[0011] Further, in step 1), the molar concentration of the pyrrole solution prepared is 0.18 mol / L, and the molar concentration of the ferric chloride solution prepared in step 1) is 0.49 mol / L;

[0012] Further, in step 2), the molar ratio of pyrrole monomer to ferric chloride is 0.36, and the volume ratio of solution A to solution B is 1:1;

[0013] The present invention also provides the advantages and uses of the above-mentioned toothbrush with PPy / PBT conductive antibacterial bristles containing PPy coating, which are specifically as follows:

[0014] The toothbrush with PPy / PBT conductive antibacterial bristles containing PPy coating of the present invention has good conductivity. When powered on, the current generated can effectively kill bacteria. Powering the toothbrush through the built-in battery can not only effectively solve the problem of bacterial growth on the bristles, but also kill the bacteria already existing in the oral cavity, thereby better protecting teeth and preventing and alleviating various oral diseases such as periodontitis and caries.

[0015] Compared with the prior art, the technical effect of the present invention is positive and obvious. The PPy coating obtained by the present invention has the advantages of excellent conductivity, low toxicity, antibacterial property through electricity, and is suitable for people of all ages, showing broad prospects in the field of antibacterial toothbrushes. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] Figure 1 This is a schematic diagram of the connection of the power-carrying device in the cyclic voltammetry conductivity study of Experimental Example 1.

[0017] Figure 2 Schematic diagram of the parameters for the cyclic voltammetry conductivity study of the PPy / PBT conductive antibacterial bristles containing PPy coating in Experimental Example 1.

[0018] Figure 3 This is a cyclic voltammetry conductivity study of the PPy / PBT conductive antibacterial bristles containing PPy coating in Experimental Example 1.

[0019] Figure 4 This is a cyclic voltammetry conductivity study of the PDA / PPy / PBT conductive bristles containing PDA / PPy coating in Experimental Example 1.

[0020] Figure 5 This is a cyclic voltammetry conductivity study of the PPy / PDA / PBT conductive bristles containing PPy / PDA coating in Experimental Example 1.

[0021] Figure 6 This is a study on the antibacterial activity of the toothbrush with PPy / PBT conductive antibacterial bristles containing PPy coating in Experimental Example 2 against Escherichia coli using the post-electric antibacterial coating method.

[0022] Figure 7 Schematic diagram of the antibacterial rate of the toothbrush with PPy / PBT conductive antibacterial bristles containing PPy coating in Experimental Example 2 using the antibacterial method after electrical antibacterial against Escherichia coli.

[0023] Figure 8 This is a study on the antibacterial activity of a toothbrush with PPy / PBT conductive antibacterial bristles containing a PPy coating in Experimental Example 3 against Staphylococcus aureus using the post-electric antibacterial coating method.

[0024] Fig. 9 Schematic diagram of the antibacterial rate of the toothbrush with PPy / PBT conductive antibacterial bristles containing PPy coating in Experimental Example 3 using the antibacterial post-electrical antibacterial method to study the antibacterial activity against Staphylococcus aureus.

[0025] Fig.10 This is a CCK-8 experimental biosafety study of the toothbrush with PPy / PBT conductive antibacterial bristles containing PPy coating in Experimental Example 4. DETAILED DESCRIPTION

[0026] The following examples are used to illustrate the present invention but are not intended to limit the scope of the present invention.

[0027] Example 1 A method for preparing a toothbrush with PPy / PBT conductive antibacterial bristles containing a PPy coating, comprising the following steps:

[0028] (1) Ultrasonic cleaning of a toothbrush in ethanol for 30 min to completely remove residual impurities. Evenly drop 1.2 g of pyrrole monomer (Py) onto the bristles of a PBT toothbrush, and then immerse the brush head in 100 mL of deionized water to form solution A. Add 8.0 g of non-hydrated ferric chloride to 100 mL of deionized water to prepare solution B. Immerse the bristle end of the toothbrush in solution A, and fully stir the entire system in an ice bath. Fully cool the two solutions in an ice bath;

[0029] (2) Slowly (about 1 drop / 2 seconds) add solution B to the bristles until all of it is added. Immerse the bristle end of the toothbrush in solution A. The in situ oxidative polymerization of pyrrole monomer on the bristle surface lasts for 3 hours, and the reaction temperature is maintained at 0°C. During the reaction, it was clearly observed that the color of the bristles changed to black, indicating that PPy was formed on the surface of the bristles. The prepared bristles were ultrasonically cleaned several times with deionized water and ethanol, and then dried in an oven to obtain PPy / PBT conductive bristles. Comparative Example 1 A toothbrush with PDA / PPy / PBT conductive bristles containing a PDA / PPy coating, which differs from Example 1 in that a PDA coating is attached to the outside of the PPy / PBT conductive antibacterial bristles. The preparation route is shown below, comprising the following steps:

[0030] (1) Ultrasonic cleaning of a toothbrush in ethanol for 30 min to completely remove residual grease and impurities. 1.2 g of pyrrole monomer (Py) was evenly added to the bristles of a PBT toothbrush, and then immersed in 100 mL of deionized water to form solution A. 8.0 g of non-hydrated ferric chloride was added to 100 mL of deionized water to prepare solution B. The bristle end of the toothbrush was immersed in solution A, and the entire system was fully stirred in an ice bath. The solution was fully cooled in an ice bath;

[0031] (2) Slowly (about 1 drop / 2 seconds) add solution B onto the bristles until all of them are added. Immerse the bristle end of the toothbrush into solution A. The in-situ oxidative polymerization of pyrrole monomer on the bristle surface lasts for 3 hours, and the reaction temperature is maintained at 0°C. During the reaction, it is clearly observed that the color of the bristles changes to black, indicating that PPy is formed on the bristle surface. The prepared bristles are ultrasonically cleaned several times with deionized water and ethanol, and then dried in an oven to obtain PPy / PBT conductive bristles;

[0032] (3) The PPy / PET conductive bristles were immersed in a 98% alkaline dopamine solution (pH = 8) and taken out after 5 hours. The prepared bristles were ultrasonically cleaned several times with deionized water and ethanol, and then dried in an oven to obtain a toothbrush with PDA / PPy / PBT conductive bristles containing a PDA / PPy coating.

[0033] Comparative Example 2 A toothbrush with PPy / PDA / PBT conductive bristles containing a PPy / PDA coating is different from Example 1 in that a PDA coating is attached between the PPy coating and the PBT of the PPy / PBT conductive antibacterial bristles. The preparation route is as follows, comprising the following steps:

[0034] (1) The toothbrush was ultrasonically cleaned in ethanol for 30 min to completely remove residual grease and impurities. 8.0 g of non-hydrated ferric chloride was added to 100 mL of deionized water to prepare solution B;

[0035] (2) Immerse the bristle end of the toothbrush in a 98% alkaline dopamine solution (pH = 8) and take it out after 5 hours. During the reaction, it is clearly observed that the bristles change color to black, indicating that PDA is formed on the surface of the bristles. The prepared bristles are ultrasonically cleaned several times with deionized water and ethanol, and then dried in an oven to obtain PDA / PBT conductive bristles;

[0036] (3) 1.2 g of pyrrole monomer (Py) was evenly dripped onto the bristles of the toothbrush, and then immersed in 100 mL of deionized water to form solution A. The entire system was fully stirred in an ice bath. The two solutions were fully cooled in an ice bath. Solution B was slowly (about 1 drop / 2 seconds) dripped onto the bristles until all of them were added. One end of the toothbrush with bristles was immersed in solution A. The in-situ oxidative polymerization of pyrrole monomer on the bristle surface lasted for 3 hours, and the reaction temperature was maintained at 0°C. The prepared bristles were ultrasonically cleaned several times with deionized water and ethanol, and then dried in an oven to obtain a toothbrush with PPy / PDA / PBT conductive bristles containing a PPy / PDA coating.

[0037] Experimental Example 1 Study on the electrical properties of a toothbrush with PPy / PBT conductive antibacterial bristles containing PPy coating using cyclic voltammetry.

[0038] Take one toothbrush each of the toothbrush with PPy / PBT conductive antibacterial bristles containing PPy coating in Example 1, the toothbrush with PDA / PPy / PBT conductive bristles containing PDA / PPy coating in Comparative Example 1, the toothbrush with PDA / PPy / PBT conductive bristles containing PPy / PDA coating in Comparative Example 2, and a blank control toothbrush. Connect the auxiliary electrode of the electrical property measurement device to the non-electrode end of a platinum electrode, connect the working electrode to the reference electrode, and then to the non-electrode end of another platinum electrode. The toothbrushes in Example 1, Comparative Example 1, and Comparative Example 2 respectively fully contact the two platinum electrodes with the front and back sides of a row of bristles in the same position and number to complete the device connection, as shown in FIG. Figure 1 As shown. Select the "Cyclic Voltammetry" option in the electrical properties measurement operating software, set the parameters "InitE(V)" to "-0.6", "High E[V]" to "0", "Low E[V]" to "0.6", "Final E[V]" to "0", "Initial Scan Polarity" to "Positive", "Scan Rate[V / s]" to "0.1", "Sweep Segments" to "4", "Sample Interval[V]" to "0.001", "QuietTime[sec]" to "2", and Sensitivity[A / V] to 1e-004, as shown. Figure 2 The measurement was started to obtain the CV graphs of the toothbrushes in Example 1, Comparative Example 1 and Comparative Example 2, respectively. Figure 3 , Figure 4 , Figure 5 As shown in the image, for a row of bristles with the same position and number, the resistance of the PPy / PBT conductive antibacterial bristles is 3428.57Ω, the resistance of the PDA / PPy / PBT conductive bristles is 18604.65Ω, and the resistance of the PPy / PDA / PBT conductive bristles is 19047.62Ω, indicating that the PPy / PBT conductive antibacterial bristles have conductivity that can be used for electrical antibacterial, and the conductivity is better than the control.

[0039] Experimental Example 2: Study on the antibacterial properties of a toothbrush with PPy / PBT conductive antibacterial bristles containing a PPy coating using the Escherichia coli coating method.

[0040] Take one toothbrush each of the PPy / PBT conductive antibacterial bristles with PPy coating in Example 1, the PDA / PPy / PBT conductive bristles with PDA / PPy coating in Comparative Example 1, the PDA / PPy / PBT conductive bristles with PPy / PDA coating in Comparative Example 2, and a blank control toothbrush, and connect the device according to the method in Experimental Example 1. Figure 1As shown. 2 microliters of liquid culture medium containing the same concentration of E. coli bacteria were dripped onto the four groups of bristles respectively, and care was taken to prevent the liquid culture medium from contacting the platinum electrode. A 1V voltage was applied to the four groups of bristles through the platinum electrode. After 300 seconds of power-on, the bacterial liquid on the four groups of bristles was fully eluted into the same volume of PBS. 100 microliters of bacterial liquid was added to each solid culture medium, and the bacterial liquid was evenly distributed on the solid culture medium by coating method. Incubated at 37°C in the dark for 12 hours, and the growth of E. coli was observed, as shown in FIG. Figure 6 The antibacterial rate of the four groups of toothbrushes when powered on is calculated, as shown in Figure 7 As shown, the comparison shows that the toothbrush with PDA / PPy / PBT conductive bristles can exhibit good antibacterial properties through electrical antibacterial, and the antibacterial property is better than the control.

[0041] Experimental Example 3 Study on the antibacterial activity of PPy / PBT conductive antibacterial bristles coated with PPy against Staphylococcus aureus by coating method.

[0042] Take one toothbrush each of the PPy / PBT conductive antibacterial bristles with PPy coating in Example 1, the PDA / PPy / PBT conductive bristles with PDA / PPy coating in Comparative Example 1, the PDA / PPy / PBT conductive bristles with PPy / PDA coating in Comparative Example 2, and a blank control toothbrush, and connect the device according to the method in Experimental Example 1. Figure 1 As shown. 2 microliters of liquid culture medium containing the same concentration of Staphylococcus aureus bacteria were dripped onto the four groups of bristles respectively, and care was taken to prevent the liquid culture medium from contacting the platinum electrode. A 1V voltage was applied to the four groups of bristles through the platinum electrode. After 300 seconds of power-on, the bacterial liquid on the four groups of bristles was fully eluted into the same volume of PBS. 100 microliters of bacterial liquid was added to each solid culture medium, and the bacterial liquid was evenly distributed on the solid culture medium by coating method. Incubated at 37°C in the dark for 12 hours, the growth of Staphylococcus aureus was observed, as shown in the figure. Figure 8 The antibacterial rate of the four groups of toothbrushes when powered on is calculated, as shown in Fig. 9 As shown, the comparison shows that the toothbrush with PDA / PPy / PBT conductive bristles can exhibit good antibacterial properties through electrical antibacterial, and the antibacterial property is better than the control.

[0043] Experimental Example 4 Study on the biosafety of a toothbrush with PPy / PBT conductive antibacterial bristles containing PPy coating.

[0044] Take one toothbrush each of the PPy / PBT conductive antibacterial bristles with PPy coating in Example 1, the PDA / PPy / PBT conductive bristles with PDA / PPy coating in Comparative Example 1, the PDA / PPy / PBT conductive bristles with PPy / PDA coating in Comparative Example 2, and a blank control toothbrush, and cut the same weight of bristles from each toothbrush. Take the same volume of complete culture medium of human umbilical vein endothelial cells in four identical centrifuge tubes, add a group of cut bristles to each centrifuge tube, fully immerse them in the culture medium, and immerse them in a 37°C, 5% CO2 incubator for 24 hours. Take three 96-well plates and mark them for 24 hours, 48 ​​hours, and 72 hours respectively. Select 16 wells on each 96-well plate and inoculate about 5,000 human umbilical vein endothelial cells. Add 100 microliters of the leaching solution of each group of bristles after 24 hours of leaching to each well where cells have been inoculated. Add the leaching solution of each group of bristles to 4 wells and place them in a 37°C, 5% CO2 incubator for incubation. The leaching solution continues to leach in the incubator. After 24 hours, take out the 96-well plate marked for 24 hours, suck out the leaching solution with a pipette, wash it with PBS, add 100 microliters of 10% CCK8 dye solution to each well where cells have been inoculated, and place it in a 37°C, 5% CO2 incubator for staining for 2 hours. Take out the 96-well plates marked for 48 hours and 72 hours, and replace the same leaching solution for each group. After staining for 2 hours, measure the absorbance of each well at a wavelength of 450nm on the 96-well plate marked for 24 hours with an enzyme marker and record the data. After 48 hours, the 96-well plate marked for 48 hours was taken out, and the CCK8 staining and absorbance measurement operation was repeated. The 96-well plate marked for 72 hours was taken out, and the leaching solution was replaced. After 72 hours, the 96-well plate marked for 72 hours was taken out, and the CCK8 staining and OD value measurement operation was repeated. The experimental data were plotted into graphs, as shown in Figure 1. Fig.10 As shown, the PPy / PBT conductive antibacterial bristles containing PPy coating have good biosafety, are non-toxic to normal cells, and have better biosafety than PDA / PPy / PBT conductive bristles containing PDA / PPy coating and PDA / PPy / PBT conductive bristles containing PPy / PDA coating.

[0045] Finally, it should be noted that the above preferred embodiments are only used to illustrate the technical solutions of the present invention rather than to limit it. Although the present invention has been described in detail through the above preferred embodiments, those skilled in the art should understand that various changes can be made in form and details without departing from the scope defined by the claims of the present invention.

Claims

1. A toothbrush with PPy / PBT conductive antibacterial bristles containing PPy coating, characterized in that It contains a PPy coating and is therefore conductive, which can be used to resist bacteria.

2. The method for preparing a toothbrush with PPy / PBT conductive antibacterial bristles containing PPy coating according to claim 1, characterized in that: The following steps are involved: (1) A step of separately preparing a pyrrole solution and a ferric chloride solution by dissolving pyrrole monomer and non-hydrated ferric chloride in water. (2) A step of oxidative polymerization of pyrrole monomers on the bristle surface is performed by chemical deposition method, wherein the pyrrole monomers are oxidized by trivalent iron ions.

3. The method for preparing a toothbrush with PPy / PBT conductive antibacterial bristles containing PPy coating according to claim 2, characterized in that: In step 1), a certain mass of pyrrole monomer (Py) is evenly added to the bristles of a PBT toothbrush, and then the brush head is immersed in a certain volume of deionized water to form a pyrrole solution. A certain mass of non-hydrated ferric chloride is added to a certain volume of deionized water to prepare a ferric chloride solution. One end of the toothbrush with bristles is immersed in the pyrrole solution, and the whole system is fully stirred in an ice bath. The two solutions are fully cooled in an ice bath to obtain.

4. The method for preparing a toothbrush with PPy / PBT conductive antibacterial bristles containing PPy coating according to claim 2, characterized in that: In step 2), solution B is slowly (less than 1 drop / second) added to the bristles until all are added. Immerse the bristle end of the toothbrush in solution A. The in-situ oxidative polymerization of pyrrole monomer on the bristle surface lasts for more than 3 hours, keeping the reaction temperature below 10°C. During the reaction, it is clearly observed that the color of the bristles changes to black, indicating that PPy is formed on the bristle surface. The prepared bristles are washed several times with deionized water and ethanol, and then dried in an oven to obtain PPy / PBT conductive bristles.

5. The method for preparing a toothbrush with PPy / PBT conductive antibacterial bristles containing PPy coating according to claim 2, characterized in that: The molar concentration of the pyrrole solution prepared in step 1) is 0.1-0.5 mol / L, and the molar concentration of the ferric chloride solution prepared in step 1) is 0.3-2.5 mol / L.

6. The method for preparing a toothbrush with PPy / PBT conductive antibacterial bristles containing PPy coating according to claim 2, characterized in that: Step 2) The molar ratio of ferric chloride to pyrrole monomer is 3-5.

7. Use of the toothbrush with PPy / PBT conductive antibacterial bristles containing PPy coating as claimed in claim 1.

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