CN115252777A

CN115252777A - In-situ whitening and anti-caries gel and preparation method thereof

Info

Publication number: CN115252777A
Application number: CN202210650346.0A
Authority: CN
Inventors: 王小磊; 廖岚; 李群; 刘锦彪; 杨学涛; 刘慧劫; 许莹莹
Original assignee: Nanchang University
Current assignee: Nanchang University
Priority date: 2022-06-09
Filing date: 2022-06-09
Publication date: 2022-11-01
Anticipated expiration: 2042-06-09
Also published as: CN115252777B

Abstract

The invention provides an in-situ whitening anticarious gel and a preparation method thereof, and provides a photoresponsive tooth whitening anticarious hydrogel and a preparation thereof, the technical scheme is that sodium alginate, bismuth nitrate pentahydrate and copper sulfate pentahydrate are used as main raw materials and are further respectively mixed with potassium chloride,Reacting sodium hydroxide, reducing agent (hydroquinone or ascorbic acid) and ethylenediamine tetraacetic acid to obtain bismuth oxychloride (Bi)₁₂O₁₇Cl₂) And cuprous oxide (Cu)₂O), introducing the sodium alginate hydrogel into a sodium alginate hydrogel system through physical adsorption to obtain a final product BC-SA. The hydrogel product contains a novel photocatalytic material Bi₁₂O₁₇Cl₂And Cu₂And O, under the irradiation of LED visible light with the wavelength of 490-540 nm, the active oxygen is generated to decompose the chromogen, and the active oxygen can also decompose extracellular polysaccharide in extracellular matrix and destroy cell membranes of planktonic bacteria to achieve the effect of decomposing bacterial plaque biological membranes, and meanwhile, the adhesion stripping effect of sodium alginate can also further remove the bacterial plaque biological membranes.

Description

In-situ whitening and anti-caries gel and preparation method thereof

Technical Field

The invention relates to the technical field of tooth whitening and tooth antibacterial and caries prevention, in particular to in-situ whitening and caries prevention gel and a preparation method thereof.

Background

The microenvironment of the oral cavity is complex and changeable, and the teeth are easily affected by various aspects, microscopically, various harmful bacteria, such as cariogenic bacteria become oral dominant flora, which can cause the teeth to be demineralized and form decayed teeth; macroscopically, food residue and the like can cause pigmentation, which affects health and beauty. The existing antibacterial agent treatment mainly used easily causes drug resistance, cannot effectively aim at carious pathogens at specific parts, easily causes oral flora micro-ecological imbalance, and the common antibacterial agent chlorhexidine mouthwash easily causes reactions such as mucous membrane coloring, allergy and the like. The existing whitening modes in clinic mainly comprise invasive treatment and non-invasive treatment. Invasive treatments include polishing and veneering, requiring cutting and grinding of the dental surface is susceptible to damage, non-invasive treatments primarily utilize peroxide (30% H)₂O₂) Under the high-intensity and large-irritation blue light (400-450 nm), a large amount of Reactive Oxygen Species (ROS) is generated. But H₂O₂The damage to the enamel is not negligible, and the damaged rough enamel is caused by the high corrosivity and the strong oxidizing property of the enamelCarious bacteria biofilm, the "chief culprit" of caries, provides a good habitat for attachment, and under the action of the vicious circle, the development of two diseases is aggravated. Therefore, the technical problem to be solved by those skilled in the art is how to provide a tooth whitening strip that can effectively resist bacteria and prevent caries, and can be used conveniently.

Disclosure of Invention

The invention aims to provide a photoresponse whitening anticarious hydrogel aiming at overcoming the technical defects in the prior art. Rapidly forming gel on the tooth surface in situ under the action of calcium ion spray, and exciting redox reaction under a healthier green light source (490-540 nm) with longer wavelength to rapidly and efficiently achieve the in situ whitening sterilization effect. The method aims to solve the defects of tooth enamel damage, sensitive pain during/after operation and the like generated in the tooth whitening process by using high-intensity bluish violet light and high-concentration hydrogen peroxide in the prior art and the problems of tooth mucous membrane coloring and flora disturbance caused by long-term use of bactericides.

In order to achieve the technical purpose, the invention adopts the following technical scheme:

a whitening anticarious gel with redox reaction excited by visible light, wherein the visible light is green light, and the green light is LED visible light with the wavelength ranging from 490 to 540 nm. Said gel comprising 1% Bi by mass of 1-4% sodium alginate₁₂O₁₇Cl₂And 0.2% of Cu₂O, said Bi₁₂O₁₇Cl₂Has an average pore size of 100-500nm₂The O particle size is about 200nm.

A preparation method of the whitening anticarious gel with the redox reaction excited by visible light comprises the following steps:

1) With Bi (NO)₃)₃·5H₂O, KCl, deionized water dosage of 2:2:3 (mmol: mmol: mL) for 30min to obtain a white suspension. Adjusting the pH value of the suspension to 12.6 by using NaOH aqueous solution (1.0 mol/L), then reacting for 24h at 160 ℃, and drying to obtain a product Bi₁₂O₁₇Cl₂。

2)CuSO₄·5H₂O, EDTA, deionized water 2:1:3 (mmol: mmol: mL) and stirred at 55 ℃ for 30min.Adding 250mL of deionized water, naOH and 1,4-hydroquinone into the solution in sequence to obtain 25:15:5 (mL: mmol) was cooled to room temperature and dried by centrifugation. The product Cu is obtained₂O。

3) Adding Bi₁₂O₁₇Cl₂、Cu₂The use amounts of O, sodium alginate and deionized water are 5:1:10:500 (g: g: g: mL) was stirred and mixed well. Obtaining the whitening anticarious hydrogel.

Preferably, the isothermal reaction at 160 ℃ in the step 1) is carried out in a high-temperature high-pressure reaction kettle.

Preferably, the isothermal reaction in step 2) is carried out under water bath conditions.

Preferably, the container in which the system is arranged is sealed by a cover during the stirring process of the step 1) and the step 2) and the constant-temperature reaction process.

Preferably, the drying conditions of step 2) are carried out under vacuum.

The invention provides a whitening anticarious hydrogel with visible light-excited redox reaction and a preparation method thereof.

Has the advantages that:

1. compared with the high-concentration peroxide used in the prior art, the whitening main material bismuth oxychloride used in the invention has small stimulation and low toxicity, and the amount of Reactive Oxygen Species (ROS) can be accurately controlled by operating a light source, so that ROS can be produced as required, and normal tissue damage can be avoided, thus achieving the effect of lossless tooth whitening.

2. Compared with the high-intensity blue light in the prior art, the LED visible light with the wavelength of 490-540 nm used in the invention has little harm to eyes and human tissues.

3. The sodium alginate is rapidly crosslinked in situ under the action of calcium ions, can be used for targeted and accurate treatment (whitening and antibiosis), can be rapidly peeled from the tooth surface, and has convenient use and small toxic and side effects.

4. The process is simple and safe, is suitable for large-scale industrial production, is convenient to use and is suitable for market popularization.

Drawings

FIG. 1: a schematic illustration of a gel cast on a tooth according to an embodiment of the present application;

FIG. 2: is a schematic diagram of the whitening effect of the gel after the gel is coated on teeth for 0-3 days in the specific embodiment of the application;

FIG. 3: is a schematic diagram of tooth surface damage in the present embodiment;

FIG. 4: the left image is an electron microscope image of the bacterial biofilm on the tooth surface, and the right image is the plate colony count.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. Approximating language, as used herein in the following examples, may be applied to represent quantitative representations that could permissibly vary in number without resulting in a change in the basic function. Accordingly, a numerical value modified by a language such as "about", "left or right" is not limited to the precise numerical value itself. In some embodiments, "about" indicates that the value allowed for correction varies within plus or minus ten percent (10%), for example, "about 100" indicates that any value between 90 and 110 is possible. Further, in the expression "about a first value to a second value", both the first and second values are corrected at about the same time. In some cases, the approximating language may be related to the precision of a measuring instrument.

Example 1

A method for preparing a photoresponsive tooth whitening anticarious gel comprises the following steps:

1) Adding about 2 parts by mass of sodium alginate into 100ml of deionized water, and swelling;

2) To the above mixture, about 1 part by mass of Bi was added₁₂O₁₇Cl₂0.2 parts by mass of Cu₂O, stirring the mixture evenly;

3) 1 mass fraction of CaCl₂Added into 100ml of deionized water to prepare a solution of about 0.1M as a cross-linking agent of the photoresponse whitening anticaries hydrogel.

4) Bi in step 2)₁₂O₁₇Cl₂From Bi (NO)₃)₃·5H₂O, KCl, deionized water dosage of 2:2:3 (mmol: mmol: mL) for 30min to obtain a white suspension. The pH of the suspension is adjusted to 12.6 by using NaOH aqueous solution (1.0 mol/L), and then the suspension is reacted at 160 ℃ for 24 hours and dried.

5) Cu in step 2)₂O is formed from CuSO₄·5H₂O, EDTA, deionized water 2:1:3 (mmol: mmol: mL) and stirred at 55 ℃ for 30min. To the above solution was added 250mL of deionized water, naOH, 1,4-hydroquinone 25:15:5 (mL: mmol) was cooled to room temperature, and the product was centrifuged and dried.

6) Coating the product obtained in the step 2) on the surface of the tooth, and using CaCl₂The solution makes the hydrogel cross-linked, the hydrogel stably stays on the tooth surface as shown in figure 1, after being irradiated for 30min by using an LED with the wavelength ranging from 490 nm to 540nm, the hydrogel is taken down, the actions are repeated twice every day, and the whitening effect is gradually remarkable as shown in figure 2. No damage to the tooth surface was seen by electron microscopy for 10 days, compared to using 30% H₂O₂Enamel lesions after 15min of treatment were severely evident. Meanwhile, the effect of removing the bacterial plaque and the biological film on the tooth surface is shown in figure 4.

As can be seen from FIG. 1, the hydrogel in example 1 is at Ca²⁺The gel can be quickly formed, is adhered to the surface of the tooth, can be torn off in a whole block after playing a role, and is convenient to use; as can be seen from fig. 2, after the gel obtained in example 1 was used, a significant whitening effect was obtained by the third day; whereas no damage to the tooth surface was observed by electron microscopy for 10 days as seen in FIG. 3, the content of 30% was used₂O₂Enamel lesions after 15min of treatment, i.e. obtained by the present applicationThe gel can achieve the effect of nondestructive whitening; as can be seen from fig. 4, the gel obtained in example 1 had a plaque biofilm removing effect, compared to the control group.

It should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.

Claims

1. A whitening anticarious gel with redox reaction stimulated by visible light, which is characterized in that the gel contains 1 percent of Bi by mass fraction of 1-4 percent of sodium alginate₁₂O₁₇Cl₂And 0.2% of Cu₂O, said Bi₁₂O₁₇Cl₂Has an average pore size of 100-500nm₂The grain diameter of O is about 200nm, and the visible light is green light.

2. A method for preparing the whitening anticaries gel of claim 1 in which redox reaction is excited by visible light, comprising the steps of:

1) With Bi (NO)₃)₃·5H₂O, KCl, deionized water dosage of 2mmol:2mmol:3mL of the solution is evenly mixed and stirred for 30min to obtain a white suspension, the pH of the suspension is adjusted to 12.6 by NaOH aqueous solution, and then the suspension reacts for 24h at 160 ℃ and is dried to obtain a product Bi₁₂O₁₇Cl₂；

2) Mixing CuSO₄·5H₂O, EDTA, deionized water 2mmol:1mmol:3mL, stirring at 55 ℃ for 30min, and adding 250mL of deionized water, naOH and 1,4-hydroquinone into the solution in sequence, wherein the mass ratio of the deionized water to the NaOH to the 1,4-hydroquinone is 25mL: 15mmol; the product Cu is obtained₂O；

3) Bi obtained in the step 1)₁₂O₁₇Cl₂And Cu₂Mixing O, sodium alginate and deionized water, wherein the proportion is 5g:1g:10g:500mL; stirring and uniformly mixing; the whitening anticarious hydrogel is obtained.

3. The method for preparing a whitening anticarious gel with a redox reaction stimulated by visible light according to claim 2, wherein the pH of the suspension in the step 1) is adjusted to 12.6, the mixture is reacted in a high-temperature high-pressure reaction kettle at 160 ℃ for 24h, and then the reaction product is dried to obtain the Bi product₁₂O₁₇Cl₂。

4. The method for preparing a whitening anticaries gel capable of exciting redox reaction by visible light according to claim 2, wherein CuSO is added in step 2)₄·5H₂O, EDTA and deionized water, stirring for 30min under the condition of water bath, and the temperature is 55 ℃.

5. The method for preparing a whitening anticarious gel with a redox reaction stimulated by visible light according to claim 2, wherein the isothermal reaction is carried out under the water bath condition after cooling to room temperature in step 2).

6. The whitening caries-preventing gel according to claim 1, wherein the green light is an LED visible light having a wavelength ranging from 490 to 540 nm.