CN107582415B - Whitening toothpaste with visible light excited oxidation-reduction reaction and preparation method thereof - Google Patents

Whitening toothpaste with visible light excited oxidation-reduction reaction and preparation method thereof Download PDF

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CN107582415B
CN107582415B CN201710655705.0A CN201710655705A CN107582415B CN 107582415 B CN107582415 B CN 107582415B CN 201710655705 A CN201710655705 A CN 201710655705A CN 107582415 B CN107582415 B CN 107582415B
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toothpaste
visible light
deionized water
reaction
hexamethylenetetramine
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CN107582415A (en
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王小磊
辛洪波
余芬
廖岚
张凤
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Nanchang University
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    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A61K8/29Titanium; Compounds thereof
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/40Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
    • A61K8/41Amines
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q11/00Preparations for care of the teeth, of the oral cavity or of dentures; Dentifrices, e.g. toothpastes; Mouth rinses
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/80Process related aspects concerning the preparation of the cosmetic composition or the storage or application thereof
    • A61K2800/81Preparation or application process involves irradiation
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/80Process related aspects concerning the preparation of the cosmetic composition or the storage or application thereof
    • A61K2800/82Preparation or application process involves sonication or ultrasonication
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/80Process related aspects concerning the preparation of the cosmetic composition or the storage or application thereof
    • A61K2800/84Products or compounds obtained by lyophilisation, freeze-drying

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  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Birds (AREA)
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  • Oral & Maxillofacial Surgery (AREA)
  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Cosmetics (AREA)

Abstract

The invention provides whitening toothpaste with visible light excited redox reaction and a preparation method thereof. The toothpaste product contains porous zinc oxide, can rapidly generate oxidation-reduction reaction on discolored teeth under the excitation of yellow light, and simultaneously has the following technical advantages: 1. has porosity and good adsorption effect. 2. Can respond to yellow light, can generate redox action without ultraviolet excitation, and is safer to use because yellow light is milder and has less stimulation to eyes. 3. The method has the advantages of simple and safe process, no need of adding organic solvent, simple operation method, low requirement on equipment and suitability for large-scale production and industrialization.

Description

Whitening toothpaste with visible light excited oxidation-reduction reaction and preparation method thereof
Technical Field
The invention relates to the technical field of toothpaste preparation, and simultaneously relates to the technical field of tooth whitening, in particular to whitening toothpaste with visible light exciting redox reaction and a preparation method thereof.
Background
Tooth whitening has become a common cosmetic requirement because the color and luster of teeth directly affect the facial appearance, and with the development of medical technology, a plurality of repair means for discolored teeth are formed in recent years, wherein the applications of covering whitening and chemical bleaching are common. The main methods of masked whitening include veneering and full crown restoration, both of which require extensive grinding of the teeth and thus irreversible damage to the structure of the teeth themselves. The chemical bleaching method is relatively safe, but depends on chemical reaction, so the reaction design is very important, and if the reactant components are not reasonable, the whitening effect is not ideal, and even side effects can be generated.
The method is characterized in that high-intensity blue light with the wavelength of 480-520 nm irradiates a reagent with hydrogen peroxide or carbamide peroxide as a main component to generate an oxidation-reduction reaction, and pigments attached to the surface and the deep layer of a tooth are removed through dentin tubules, so that the whitening effect is achieved. Although this method has shown a good tooth-cleaning effect, there are side effects such as enamel demineralization, soft tissue irritation, tooth sensitivity, acute pulpitis, etc. in practical use because the reactive ingredients are not safe enough. Furthermore, since blue light is more irritating to the eye, prolonged application may cause lesions in the user's lens, in which case it would be desirable to improve the safety of such methods if a combination of reactants catalyzed by mild light could be developed.
Disclosure of Invention
The invention aims to provide whitening toothpaste with oxidation-reduction reaction excited by visible light and a preparation method thereof aiming at overcoming the technical defects in the prior art, and aims to solve the technical problem that the whitening effect is poor due to unreasonable reactant design in the prior art for tooth bleaching by photocatalytic oxidation reaction.
Another technical problem to be solved by the present invention is that tooth bleaching by photocatalytic oxidation in the prior art has damage to enamel due to unreasonable design of reactants.
The invention also aims to solve the technical problem that tooth bleaching by photocatalytic oxidation reaction in the prior art can only be carried out under the excitation of blue light or ultraviolet rays, and the light has strong irritation to human bodies.
In order to achieve the technical purpose, the invention adopts the following technical scheme:
a whitening toothpaste capable of exciting redox reaction by visible light, wherein the visible light is yellow light, the toothpaste contains porous zinc oxide with the mass fraction of 3%, the average pore diameter of the porous zinc oxide is 5 μm, and the average particle size of the porous zinc oxide is 15 μm. In the technical scheme, the yellow light is strictly limited to light with the wavelength ranging from 580nm to 595 nm.
A preparation method of the whitening toothpaste with the oxidation-reduction reaction excited by visible light comprises the following steps:
1) with Zn (NO)3)2·6H2O、NH3·H2The amount of the four components of O, hexamethylenetetramine and deionized water is 10:16:5:20(mmol: mmol: m L) and Zn (NO) is added3)2·6H2O、NH3·H2Dissolving O and hexamethylenetetramine in deionized water, and stirring for 10 min;
2) then reacting the product obtained in the step 1) for 15min at a constant temperature of 65 ℃;
3) adding sodium citrate and hydroxypropyl methyl cellulose into the sodium citrate, hydroxypropyl methyl cellulose and deionized water in the step 1) according to the proportion of 0.14:0.1:100(g: g: m L), and reacting at the constant temperature of 85 ℃ for 12 hours;
4) and then, carrying out vacuum freeze drying on the product obtained in the step 3), and then placing the product into a microwave oven for microwave treatment for 15min to obtain the whitening toothpaste with visible light excited redox reaction.
Preferably, Zn (NO) in step 1)3)2·6H2O、NH3·H2The adding sequence of O and hexamethylenetetramine to the deionized water is NH in sequence3·H2O、Zn(NO3)2·6H2O, hexamethylene tetramine.
Preferably, the isothermal reaction in step 2) and the isothermal reaction in step 3) are both performed under water bath conditions.
Preferably, the container in which the system is arranged is sealed by a cover in the stirring process in the step 1) and the constant-temperature reaction process in the step 2).
Preferably, step 1) is performed after stirring for 10min until the solution is clear, and step 2) is performed.
The other whitening toothpaste is formed by exciting a redox reaction by visible light, wherein the visible light is blue light, and the toothpaste contains 5% of titanium dioxide by mass. In the technical scheme, the blue light is strictly defined as light with the wavelength within the range of 450-480 nm.
A preparation method of the whitening toothpaste with the oxidation-reduction reaction excited by visible light comprises the following steps:
1) uniformly mixing the nano titanium dioxide, the dopamine hydrochloride and the pure water in a container according to the proportion of 0.08:1:50(g: g: m L);
2) adding hexamethylene tetramine into the mixture, ultrasonically oscillating for 5min, sealing the container, and then carrying out water bath for 3h at 90 ℃; the addition amount of the hexamethylene tetramine is 10 times of the weight of the dopamine hydrochloride in the step 1);
3) washing the product obtained in the step 2) with pure water for 2 times, then washing with absolute ethyl alcohol for 2 times, then washing with pure water for 2 times, and freeze-drying to obtain the whitening toothpaste with visible light excited redox reaction.
Preferably, the container in step 1) is a conical flask.
Preferably, the toothpaste can be directly dissolved in water for use, and can also be prepared into gel, paste and the like by adding pharmaceutical excipients.
In the above technical scheme, the visible light-excited redox reaction is a photocatalytic reaction, and specifically belongs to an oxidation reaction catalyzed by visible light.
The invention provides whitening toothpaste with visible light excited redox reaction and a preparation method thereof. The toothpaste product contains porous zinc oxide, can rapidly generate oxidation-reduction reaction on discolored teeth under the excitation of yellow light, and simultaneously has the following technical advantages: 1. has porosity and good adsorption effect. 2. Can respond to yellow light, can generate redox action without ultraviolet excitation, and is safer to use because yellow light is milder and has less stimulation to eyes. 3. The method has the advantages of simple and safe process, no need of adding organic solvent, simple operation method, low requirement on equipment and suitability for large-scale production and industrialization.
In addition, the invention further provides another whitening toothpaste which is formed by exciting redox reaction by visible light and a preparation method thereof. The toothpaste product takes titanium dioxide as a main whitening agent, can quickly generate oxidation-reduction reaction on discolored teeth under the excitation of blue light, and simultaneously has the following technical advantages: 1. can respond to visible light, can generate oxidation-reduction action without ultraviolet excitation, and is more healthy and safe. 2. The method has the advantages of simple and safe process, no need of adding organic solvent, simple operation method, low equipment requirement and suitability for large-scale production and industrialization.
Drawings
FIG. 1 is a graph showing the results of an experiment in example 3 of the present invention; wherein, part a is a real object diagram of a toothbrush (which can be used with the toothpaste of the invention) capable of emitting yellow light; parts b to d are respectively a whitening effect graph of the toothpaste prepared in the example 1 after the toothpaste is used for treating experimental teeth for different action time; the insets at the upper right corners of the parts b to d are colony growth diagrams obtained by plating the substances on the surfaces of the experimental teeth; section e is a scanning electron micrograph of the tooth enamel in section b; part f is a scanning electron micrograph of the tooth enamel in part d, and part g is a scanning electron micrograph of the tooth enamel after 3h treatment with a conventional cold light whitening method; section h is a partial enlarged view at a frame in section e; part i is a partial enlarged view at a frame in part f; the portion j is a partially enlarged view of the portion g at the frame.
FIG. 2 is a graph showing the results of an experiment in example 4 of the present invention; wherein, a part a is a whitening effect graph of the toothpaste prepared in the example 2 after the toothpaste is used for treating experimental teeth for different action time; section b is a scanning electron micrograph of experimental tooth enamel 4h after treatment without treatment and with the toothpaste prepared in example 2, respectively.
Detailed Description
Hereinafter, specific embodiments of the present invention will be described in detail. Well-known structures or functions may not be described in detail in the following embodiments in order to avoid unnecessarily obscuring the details.
Approximating language, as used herein in the following examples, may be applied to identify 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.
Unless defined otherwise, technical and scientific terms used in the following examples have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
Example 1
1. The precursor solution was prepared from 50mM zinc nitrate hexahydrate (Zn (NO)3)2·6H2O), 80mM ammonia (NH)3·H2O) and 25mM Hexamethylenetetramine (HMT) in 100ml deionized water, covering the container with a cover, fully stirring for 10min until the solute is completely dissolved and clarified for later use, and adding NH in the order to avoid the precursor solution from generating early precipitation3·H2O、Zn(NO3)2·6H2O, HMT and the container is always sealed with a lid.
2. When the temperature of the water bath kettle reaches 65 ℃, the precursor liquid container covered with the cover is put into the water bath kettle and is ensured to be fully immersed, and the reaction lasts for 15 min.
3. 0.14g of sodium citrate and 0.1g of hydroxypropyl methyl cellulose are respectively added into the solution, and the mixture is put into a water bath kettle at 85 ℃ for reaction for 12 hours.
4. And putting the obtained product into a vacuum freeze dryer, drying, and putting into a household microwave oven for pyrolysis for 15min to obtain a finished product.
Example 2
1. Putting 0.08g of nano titanium dioxide and 0.01g of dopamine hydrochloride into a 100ml conical flask, adding 50ml of pure water, and uniformly mixing by oscillation;
2. adding 0.1g of hexamethylenetetramine, ultrasonically oscillating for 5min, sealing the container, and then putting the container into a water bath kettle at 90 ℃ for reaction for 3 h;
3. washing the obtained product with pure water for 2 times, washing with anhydrous ethanol for 2 times, washing with pure water for 2 times, putting the product into a vacuum freeze dryer, and freeze-drying to obtain the final product.
Example 3
The whitening effect can be seen by dissolving the product of example 1 in water, dipping the solution in a toothbrush, turning on L ED yellow light, and brushing teeth for three minutes.
Meanwhile, the test teeth were treated with the toothpaste prepared in example 1 for various periods of time by immersing the test teeth in the aqueous solution of the toothpaste prepared in example 1 and continuously irradiating with L ED yellow light, and the test results are shown in FIG. 1.
As shown in the parts b-d of fig. 1, the treatment effect is obvious after half an hour, and the tooth stain in the tooth socket is well cleaned. As can be seen from the interpolated graphs in the upper right corners of each of b-d. The teeth treated by the toothpaste in the embodiment 1 have almost no bacteria growing on the surface, and can effectively inhibit the breeding of oral bacteria. As shown in fig. 1, sections e to j, it can be seen from the scanning electron microscope that the toothpaste of example 1 has almost no damage to enamel even after 3 hours of treatment, and the damage of enamel is clearly seen on the tooth surface treated with the cold light whitening under the same conditions, and thus the toothpaste provided in example 1 is safe and effective.
Example 4
The whitening effect can be seen by dissolving the finished product of example 2 in water, dipping the solution with a toothbrush, turning on L ED blue light, and brushing teeth for three minutes.
Meanwhile, the experimental teeth were treated with the toothpaste prepared in example 2 for various times by immersing the experimental teeth in the aqueous solution of the toothpaste prepared in example 2 and continuously irradiating with L ED blue light, and the experimental results are shown in fig. 2.
As shown in a part of fig. 2, after the titanium dioxide is treated by blue light irradiation, a whitening effect is remarkably achieved in a half hour. As shown in part b of fig. 2, no significant change was observed in the enamel surface over 4 hours, and thus it was seen that the toothpaste provided in example 2 was safe and effective.
The embodiments of the present invention have been described in detail, but the description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention. Any modification, equivalent replacement, and improvement made within the scope of the application of the present invention should be included in the protection scope of the present invention.

Claims (5)

1. A whitening toothpaste with an oxidation-reduction reaction excited by visible light is characterized in that the visible light is yellow light, the toothpaste contains 3% by mass of porous zinc oxide, the average pore diameter of the porous zinc oxide is 5 μm, and the average particle diameter of the porous zinc oxide is 15 μm;
the preparation method of the toothpaste comprises the following steps:
1) with Zn (NO)3)2·6H2O、NH3·H2The amount of the four components of O, hexamethylenetetramine and deionized water is 10mmol, 16mmol, 5mmol and 20m L, and Zn (NO) is added3)2·6H2O、NH3·H2Dissolving O and hexamethylenetetramine in deionized water, and stirring for 10 min;
2) then reacting the product obtained in the step 1) for 15min at a constant temperature of 65 ℃;
3) adding sodium citrate and hydroxypropyl methyl cellulose into the sodium citrate, hydroxypropyl methyl cellulose and the deionized water in the step 1) according to the proportion of 0.14g:0.1g:100m L, and reacting at the constant temperature of 85 ℃ for 12 hours;
4) and then, carrying out vacuum freeze drying on the product obtained in the step 3), and then placing the product into a microwave oven for microwave treatment for 15min to obtain the whitening toothpaste with visible light excited redox reaction.
2. A method for preparing whitening toothpaste according to claim 1, wherein the visible light excites the redox reaction, comprising the steps of:
1) with Zn (NO)3)2·6H2O、NH3·H2The amount of the four components of O, hexamethylenetetramine and deionized water is 10mmol, 16mmol, 5mmol and 20m L, and Zn (NO) is added3)2·6H2O、NH3·H2Dissolving O and hexamethylenetetramine in deionized water, and stirring for 10 min;
2) then reacting the product obtained in the step 1) for 15min at a constant temperature of 65 ℃;
3) adding sodium citrate and hydroxypropyl methyl cellulose into the sodium citrate, hydroxypropyl methyl cellulose and the deionized water in the step 1) according to the proportion of 0.14g:0.1g:100m L, and reacting at the constant temperature of 85 ℃ for 12 hours;
4) and then, carrying out vacuum freeze drying on the product obtained in the step 3), and then placing the product into a microwave oven for microwave treatment for 15min to obtain the whitening toothpaste with visible light excited redox reaction.
3. The method according to claim 2, wherein Zn (NO) in step 1)3)2·6H2O、NH3·H2The adding sequence of O and hexamethylenetetramine to the deionized water is NH in sequence3·H2O、Zn(NO3)2·6H2O, hexamethylene tetramine.
4. The method according to claim 2, wherein the isothermal reaction in step 2) and the isothermal reaction in step 3) are performed under water bath conditions.
5. The method according to claim 2, wherein the container in which the system is located is sealed by a cover during the stirring in step 1) and the isothermal reaction in step 2).
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CN110464674A (en) * 2019-08-19 2019-11-19 南京理工大学 Tooth whitening products containing piezoelectric material
CN111494230B (en) * 2020-04-30 2021-09-17 江西师范大学 Cold light tooth whitening gel, preparation method and application
CN111646495A (en) * 2020-06-24 2020-09-11 南昌大学 Double-light response type zinc oxide, preparation method thereof and photosensitive coating with antibacterial osteogenesis property
CN112957385A (en) * 2021-04-30 2021-06-15 镇江市许布医疗器械有限公司 Preparation process of carbonized moxa/zinc oxide composite material with near-infrared light/yellow light responsiveness and responsiveness determination method thereof
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