CN114732749A

CN114732749A - Anti-ultraviolet and anti-blue-light carbon quantum dot and preparation method and application thereof

Info

Publication number: CN114732749A
Application number: CN202210225724.0A
Authority: CN
Inventors: 刘应亮; 王睿哲; 胡广齐; 胡超凡; 庄健乐; 雷炳富; 张学杰; 李唯; 张浩然; 郑明涛; 董汉武; 肖勇; 梁业如; 胡航
Original assignee: Guangdong Carbon Purple Technology Co ltd
Current assignee: Guangdong Carbon Purple Technology Co ltd
Priority date: 2022-03-07
Filing date: 2022-03-07
Publication date: 2022-07-12
Anticipated expiration: 2042-03-07
Also published as: CN114732749B

Abstract

The invention relates to the technical field of new materials, in particular to an anti-ultraviolet and anti-blue-light carbon quantum dot and a preparation method thereof, wherein the carbon quantum dot consists of an ultraviolet absorbent and a nitrogen-containing organic matter, can be used as the ultraviolet absorbent and the blue-light absorbent, and has the advantages of good skin-friendly effect, low biotoxicity and good biocompatibility; the preparation method of the anti-ultraviolet and anti-blue-light carbon quantum dot has the advantages of easiness in operation, lower cost and high yield.

Description

Anti-ultraviolet and anti-blue-light carbon quantum dot and preparation method and application thereof

Technical Field

The invention relates to the technical field of new materials, in particular to an ultraviolet and blue light resistant carbon quantum dot and a preparation method and application thereof.

Background

Exposure to ultraviolet radiation that is too high for an individual's skin type can result in sunburn. Ranging from a brief mild redness of the skin to painful blisters lasting several days. Other inflammatory reactions of the skin (photodermatosis) occur in people who are abnormally sensitive to ultraviolet radiation. Prolonged exposure to uv radiation damages structural proteins in the dermis (e.g., elastin and collagen), causing wrinkles and typical photoaging, a major environmental risk factor for many skin cancers.

A common way to prevent uv light is to use uv absorbers. Existing ultraviolet absorbers include physical absorbers and chemical absorbers. Although the physical absorbent has a good ultraviolet absorption effect, the physical absorbent has large particles, and is easy to generate the problems of aggregation, uneven distribution and the like, thereby causing the problems of whitening and the like; although the chemical absorbent has good use feeling, the ultraviolet absorption range is narrow, the ultraviolet in the wave band of 300nm-400nm is difficult to be completely absorbed, and the chemical absorbent is generally organic matter, has certain toxicity and certain harm to human bodies.

In addition, most of the existing ultraviolet absorbers can not absorb blue light, and researches show that the wave band of the blue light is 400-500nm, the wave band is the shortest part in the visible light wave band and is also the part with the highest energy in the visible light, but as the wave length is further shortened, the penetration capacity of the ultraviolet absorbers is stronger, the transmittance of the ultraviolet absorbers to human eyes is higher, and meanwhile, the retina in the human eyes has an absorption peak in the blue light region, so that the short-wave blue light has certain harm to the human eyes. Moreover, the relatively low-energy long-wave blue light (480-500nm) can also play a role in regulating the biological rhythm, and the excessive exposure of the blue light can damage the physiological rhythm of people, thereby causing the problems of insomnia and the like.

Therefore, the existing ultraviolet absorbent can not prevent the damage of blue light to human body.

Disclosure of Invention

One of the purposes of the invention is to provide a carbon quantum dot capable of preventing ultraviolet and blue light by avoiding the defects of the prior art, and the carbon quantum dot has the advantages of good skin-friendly effect, low biotoxicity and good biocompatibility.

The second purpose of the invention is to provide a preparation method of the ultraviolet and blue light resistant carbon quantum dot.

The invention also aims to provide an application of the carbon quantum dots.

One of the purposes of the invention is realized by the following technical scheme:

provides a carbon quantum dot for preventing ultraviolet and blue light, which consists of an ultraviolet absorbent and a nitrogen-containing organic matter.

In some embodiments, the weight ratio of the uv absorber to the nitrogen-containing organic compound is 0.2 to 2: 0.1 to 5.

In some embodiments, the ultraviolet absorber is phenyl ortho-hydroxybenzoate, 2, 4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, resorcinol monobenzoate, 2- (2 '-hydroxy-5' -methylphenyl) benzotriazole, 2-hydroxy-4-octyloxybenzophenone, 2- (2 '-hydroxy-3', 5 '-di-tert-phenyl) -5-chlorobenzotriazole, tris (1, 2, 2, 6, 6-pentamethylpiperidinyl) phosphite, 4-benzoyloxy-2, 2, 6, 6-tetramethylpiperidine, 2, 4, 6-tris (2' n-butoxyphenyl) -1, 3, 5-triazine or a mixture of at least two ultraviolet absorbers.

In some embodiments, the nitrogen-containing organic compound is any one of urea, glutamic acid, barbituric acid, melamine, lysine, methylamine, ethylamine, ethylenediamine, ethanolamine, EDTA, aspartic acid, N-propylamine, isopropylamine, cyclohexylamine, benzylamine, N-dimethylaniline, or a mixture of at least two nitrogen-containing organic compounds.

The anti-ultraviolet and anti-blue-light carbon quantum dot has the beneficial effects that:

(1) the carbon quantum dot is composed of an ultraviolet absorbent and a nitrogen-containing organic matter, and the ultraviolet absorbent has an ultraviolet absorption function, so that the carbon quantum dot has an ultraviolet absorption function; after the ultraviolet absorbent and the nitrogenous organic matter are combined, the carbon quantum dots can also be used as blue light absorbent, namely, the carbon quantum dots also have the function of absorbing blue light, so that the carbon quantum dots can absorb ultraviolet light and blue light.

(2) The carbon quantum dots are zero-dimensional nano materials, and the diameter of the carbon quantum dots is smaller than 10nm of spherical particles and far smaller than zinc oxide and titanium dioxide powder particles commonly used in physical ultraviolet protection, so that the ultraviolet protection materials have good skin feel; meanwhile, the carbon quantum dots have lower biotoxicity and excellent biocompatibility, and compared with chemical ultraviolet-proof substances, the carbon quantum dots are milder, and the second purpose of the invention is realized by the following technical scheme:

provides a preparation method of a UV-and blue-resistant carbon quantum dot, which is used for preparing the UV-and blue-resistant carbon quantum dot and comprises the following steps,

s1, mixing the ultraviolet absorbent with the nitrogenous organic matter and dissolving the mixture in absolute ethyl alcohol to obtain a mixed solution;

s2, reacting the mixed solution in a reaction kettle at 160-240 ℃ for 4-10 h, filtering the mixed solution in the reaction kettle after the reaction is finished and the reaction kettle is cooled to room temperature, and collecting filtrate;

s3, adding deionized water into the filtrate to obtain a turbid liquid containing yellow precipitates;

and S4, collecting yellow precipitate in the turbid liquid, washing and drying the yellow precipitate, wherein the yellow precipitate is an anti-ultraviolet and blue-light carbon quantum dot.

In some embodiments, in S2, the mixed solution is filtered with a 0.22 μm microfiltration membrane.

In the S4, the turbid solution is centrifuged to collect a yellow precipitate.

In some embodiments, in S4, the yellow precipitate is washed with deionized water 2-3 times, and the washed yellow precipitate is dried in a freeze dryer to obtain a dried yellow powder.

In some embodiments, in S1, the solution in which the ultraviolet absorber and the nitrogen-containing organic substance are dissolved is subjected to ultrasonic treatment for 2-10 min to obtain a mixed solution.

The preparation method of the anti-ultraviolet and anti-blue-light carbon quantum dot has the beneficial effects that:

the preparation method of the invention makes the ultraviolet absorbent react with the nitrogenous organic matter to prepare the novel carbon quantum dot, so that the carbon quantum dot can be used as the ultraviolet absorbent and the blue light absorbent.

The invention also provides application of the carbon quantum dots in manufacturing ultraviolet-proof and blue-light-proof products.

In the application, the carbon quantum dots have the effects of absorbing ultraviolet light and absorbing blue light, so that the effects of absorbing ultraviolet light and absorbing blue light of the product can be realized when the carbon quantum dots are applied to the product.

Drawings

The invention is further described with the aid of the accompanying drawings, in which the embodiments do not constitute any limitation to the invention, and for a person skilled in the art, without inventive effort, further drawings may be derived from the following figures.

FIG. 1 is an ultraviolet absorption spectrum of a carbon quantum dot prepared in an example of the present invention.

Detailed Description

Preferred embodiments of the present invention will be described in more detail below with reference to the accompanying drawings. While the preferred embodiments of the present invention are shown in the drawings, it should be understood that the present invention may be embodied in various forms and should not be limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art.

The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used in this specification and the appended claims, the singular forms "a", "an", and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise. It should also be understood that the term "and/or" as used herein refers to and encompasses any and all possible combinations of one or more of the associated listed items.

It is to be understood that, although the terms first, second, third, etc. may be used herein to describe various information, such information should not be limited by these terms. These terms are only used to distinguish one type of information from another. For example, first information may also be referred to as second information, and similarly, second information may also be referred to as first information, without departing from the scope of the present invention. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of the present invention, "a plurality" means two or more unless specifically defined otherwise.

Example 1

The ultraviolet and blue light resistant carbon quantum dot disclosed in this embodiment is composed of an ultraviolet absorbent and a nitrogen-containing organic substance, wherein a weight ratio of the ultraviolet absorbent to the nitrogen-containing organic substance is 0.2: 0.5.

the carbon quantum dots are composed of ultraviolet absorbers and nitrogenous organic matters, and can be used as ultraviolet absorbers for absorbing ultraviolet rays in all bands and blue light absorbers for absorbing blue light. Moreover, the carbon quantum dots are zero-dimensional nano materials, and spherical particles with the diameter less than 10nm are far smaller than zinc oxide and titanium dioxide powder particles commonly used in physical sunscreen cream, so that the carbon quantum dots have good skin feel; meanwhile, the carbon quantum dots have low biotoxicity, excellent biocompatibility and better mildness.

The preparation method of the anti-ultraviolet and anti-blue-light carbon quantum dot comprises the following steps, wherein 2, 4-dihydroxy benzophenone is selected as an ultraviolet absorbent, barbituric acid is selected as a nitrogen-containing organic matter,

s1, mixing 0.2g of ultraviolet absorbent with 0.5g of nitrogenous organic matter, and dissolving in 50ml of absolute ethyl alcohol to obtain a mixed solution;

s2, reacting the mixed solution in a reaction kettle with a polytetrafluoroethylene lining for 4 hours at 160 ℃, filtering the mixed solution in the reaction kettle after the reaction is finished and the reaction kettle is cooled to room temperature, and collecting filtrate;

In the above preparation steps, the ultraviolet absorbent is combined with the nitrogen-containing organic substance, thereby preparing ultraviolet that can absorb both ultraviolet and blue light.

In this example, in the step S2, the mixed solution was filtered through a 0.22 μm microfiltration membrane. The 0.22 mu m microporous filter membrane has good filtering effect, can effectively remove large particles in the mixed solution and ensure that the particle size of solid substances in the mixed solution is smaller. Of course, other filtering means can be used, without limitation.

In this embodiment, in S4, the turbid solution is centrifuged to collect a yellow precipitate. Wherein the turbid solution is centrifuged by a centrifuge at 10000 r/min. Of course, other collection methods can be used, and are not limited herein.

In this embodiment, in S4, the yellow precipitate is washed with deionized water 2 to 3 times, and the washed yellow precipitate is put into a freeze dryer to be dried, so as to obtain a dried yellow powder.

In this embodiment, in S1, the solution in which the ultraviolet absorber and the nitrogen-containing organic substance are dissolved is subjected to ultrasonic treatment for 7min to obtain a mixed solution. Ultrasonically vibrating the solution helps to improve mixing uniformity.

Example 2

The ultraviolet and blue light resistant carbon quantum dot disclosed in this embodiment is composed of an ultraviolet absorbent and a nitrogen-containing organic substance, wherein a weight ratio of the ultraviolet absorbent to the nitrogen-containing organic substance is 2: 5.

The preparation method of the anti-ultraviolet and anti-blue-light carbon quantum dot comprises the following steps, wherein the ultraviolet absorbent is phenyl o-hydroxybenzoate, the nitrogen-containing organic matter is melamine,

s1, mixing 2g of ultraviolet absorbent with 5g of nitrogenous organic matter and dissolving in 100ml of absolute ethyl alcohol to obtain a mixed solution;

s2, reacting the mixed solution in a reaction kettle with a polytetrafluoroethylene lining at 240 ℃ for 10 hours, filtering the mixed solution in the reaction kettle after the reaction is finished and the reaction kettle is cooled to room temperature, and collecting filtrate;

In this embodiment, in S4, the turbid solution is centrifuged to collect a yellow precipitate. Wherein the turbid solution is centrifuged at 10000r/min by a centrifuge. Of course, other collection methods can be used, and are not limited herein.

In this embodiment, in S1, a solution in which an ultraviolet absorber and a nitrogen-containing organic substance are dissolved is subjected to ultrasonic treatment for 2min to obtain a mixed solution. Ultrasonically vibrating the solution helps to improve mixing uniformity.

Example 3

The ultraviolet and blue light resistant carbon quantum dot disclosed in this embodiment is composed of an ultraviolet absorbent and a nitrogen-containing organic substance, wherein a weight ratio of the ultraviolet absorbent to the nitrogen-containing organic substance is 1: 1.

The preparation method of the anti-ultraviolet and blue-light carbon quantum dots comprises the following steps of selecting 2- (2 '-hydroxy-5' -methylphenyl) benzotriazole as an ultraviolet absorbent, selecting lysine as a nitrogen-containing organic substance,

s1, mixing 1g of ultraviolet absorbent with 1g of nitrogen-containing organic matter, and dissolving in 120ml of absolute ethyl alcohol to obtain a mixed solution;

s2, reacting the mixed solution in a reaction kettle with a polytetrafluoroethylene lining at 200 ℃ for 6 hours, filtering the mixed solution in the reaction kettle after the reaction is finished and the reaction kettle is cooled to room temperature, and collecting filtrate;

and S4, collecting yellow precipitate in the turbid liquid, washing and drying the yellow precipitate, wherein the yellow precipitate is a carbon quantum dot for resisting ultraviolet and blue light.

In this embodiment, in S1, the solution in which the ultraviolet absorber and the nitrogen-containing organic substance are dissolved is subjected to ultrasonic treatment for 8min to obtain a mixed solution. Ultrasonic vibration of the solution helps to improve mixing uniformity.

Example 4

The ultraviolet and blue light resistant carbon quantum dot disclosed in this embodiment is composed of an ultraviolet absorbent and a nitrogen-containing organic substance, wherein a weight ratio of the ultraviolet absorbent to the nitrogen-containing organic substance is 0.5: 1.

The preparation method of the anti-ultraviolet and blue-light carbon quantum dot comprises the following steps of selecting resorcinol monobenzoate as an ultraviolet absorbent, selecting methylamine as a nitrogen-containing organic matter,

s1, mixing 0.5g of ultraviolet absorbent with 1g of nitrogenous organic matter and dissolving in 50ml of absolute ethyl alcohol to obtain a mixed solution;

s2, reacting the mixed solution in a reaction kettle with a polytetrafluoroethylene lining at 220 ℃ for 8 hours, filtering the mixed solution in the reaction kettle after the reaction is finished and the reaction kettle is cooled to room temperature, and collecting filtrate;

In this embodiment, in S1, the solution in which the ultraviolet absorber and the nitrogen-containing organic substance are dissolved is subjected to ultrasonic treatment for 10min to obtain a mixed solution. Ultrasonically vibrating the solution helps to improve mixing uniformity.

Example 5

This example is different from example 1 in that the ultraviolet absorber can be any one of 2, 4-dihydroxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2- (2 '-hydroxy-3', 5 '-di-tert-phenyl) -5-chlorobenzotriazole, tris (1, 2, 2, 6, 6-pentamethylpiperidinyl) phosphite, 4-benzoyloxy-2, 2, 6, 6-tetramethylpiperidine, 2, 4, 6-tris (2' n-butoxyphenyl) -1, 3, 5-triazine, or a mixture of at least two ultraviolet absorbers, and other implementation steps are the same as example 1 and are not repeated herein.

Example 6

The difference between this embodiment and embodiment 1 is that the nitrogen-containing organic substance can be any one of nitrogen-containing organic substances of urea, glutamic acid, ethylamine, ethylenediamine, ethanolamine, EDTA, aspartic acid, N-propylamine, isopropylamine, cyclohexylamine, benzylamine, and N, N-dimethylaniline, or a mixture of at least two of nitrogen-containing organic substances, and other implementation steps are the same as those in embodiment 1 and are not described herein again.

Example 7

This example provides the use of the carbon quantum dots of example 1: placing a beaker in a dark environment, respectively adding 30g of face cream and 5% of carbon quantum dot powder in the embodiment 1 by mass of the face cream, and stirring at 1000rpm for 10 hours to obtain a uniformly mixed sun cream product. Of course, the carbon quantum dots of example 1 can also be applied to the manufacture of other products, and are not limited herein.

And (3) performance detection:

the ultraviolet absorption spectrum of the carbon quantum dot prepared in example 1 was examined, including the steps of: the yellow precipitate obtained in example 1 was pulverized into powder, and the ultraviolet spectrum of the yellow precipitate (carbon quantum dots) powder of example 1 was measured by a U3900 ultraviolet visible transmission spectrometer of hitachi corporation to obtain an ultraviolet absorption spectrum shown in fig. 1. As can be seen from fig. 1: the carbon quantum dot powder prepared in example 1 has a wide absorption peak at 250-450nm, which covers the whole ultraviolet light band and short-wave blue light band, and thus, the carbon quantum dot prepared in example 1 can absorb ultraviolet light and blue light simultaneously.

The relative arrangement of the components and steps, the numerical expressions, and numerical values set forth in these embodiments do not limit the scope of the present application unless specifically stated otherwise. Meanwhile, it should be understood that the sizes of the respective portions shown in the drawings are not drawn in an actual proportional relationship for the convenience of description. Techniques, methods, and apparatus known to those of ordinary skill in the relevant art may not be discussed in detail but are intended to be part of the specification where appropriate. In all examples shown and discussed herein, any particular value should be construed as merely illustrative, and not limiting. Thus, other examples of the exemplary embodiments may have different values. It should be noted that: like reference numbers and letters refer to like items in the following figures, and thus, once an item is defined in one figure, it need not be discussed further in subsequent figures.

In the description of the present application, it is to be understood that the orientation or positional relationship indicated by the directional terms such as "front, rear, upper, lower, left, right", "lateral, vertical, horizontal" and "top, bottom", etc., are generally based on the orientation or positional relationship shown in the drawings, and are used for convenience of description and simplicity of description only, and in the case of not making a reverse description, these directional terms do not indicate and imply that the device or element being referred to must have a particular orientation or be constructed and operated in a particular orientation, and therefore, should not be considered as limiting the scope of the present application; the terms "inner and outer" refer to the inner and outer relative to the profile of the respective component itself.

Spatially relative terms, such as "above … …," "above … …," "above … … surface," "above," and the like, may be used herein for ease of description to describe one device or feature's spatial relationship to another device or feature as illustrated in the figures. It will be understood that the spatially relative terms are intended to encompass different orientations of the device in use or operation in addition to the orientation depicted in the figures. For example, if a device in the figures is turned over, devices described as "above" or "on" other devices or configurations would then be oriented "below" or "under" the other devices or configurations. Thus, the exemplary term "above … …" can include both an orientation of "above … …" and "below … …". The device may be otherwise variously oriented (rotated 90 degrees or at other orientations) and the spatially relative descriptors used herein interpreted accordingly.

It should be noted that the terms "first", "second", and the like are used to define the components, and are only used for convenience of distinguishing the corresponding components, and the terms have no special meanings unless otherwise stated, and therefore, the scope of protection of the present application is not to be construed as being limited.

The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims

1. An anti-ultraviolet and anti-blue carbon quantum dot is characterized in that: consists of ultraviolet absorbent and nitrogen-containing organic matter.

2. The uv-and blue-shielding carbon quantum dot as claimed in claim 1, wherein: the weight ratio of the ultraviolet absorbent to the nitrogen-containing organic matter is 0.2-2: 0.1 to 5.

3. The uv-and blue-shielding carbon quantum dot as claimed in claim 1, wherein: the ultraviolet absorbent is phenyl ortho-hydroxybenzoate, 2, 4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, resorcinol monobenzoate, 2- (2 '-hydroxy-5' -methylphenyl) benzotriazole, 2-hydroxy-4-octyloxybenzophenone, 2- (2 '-hydroxy-3', 5 '-di-tert-phenyl) -5-chlorobenzotriazole, tris (1, 2, 2, 6, 6-pentamethylpiperidinyl) phosphite, 4-benzoyloxy-2, 2, 6, 6-tetramethylpiperidine, 2, 4, 6-tris (2' n-butoxyphenyl) -1, 3, 5-triazine or a mixture of at least two ultraviolet absorbers.

4. The uv-and blue-shielding carbon quantum dot as claimed in claim 1, wherein: the nitrogen-containing organic matter is any one of urea, glutamic acid, barbituric acid, melamine, lysine, methylamine, ethylamine, ethylenediamine, ethanolamine, EDTA, aspartic acid, N-propylamine, isopropylamine, cyclohexylamine, benzylamine and N, N-dimethylaniline or a mixture of at least two nitrogen-containing organic matters.

5. A preparation method of an anti-ultraviolet and anti-blue-light carbon quantum dot is characterized by comprising the following steps: preparing the UV and blue light-shielding carbon quantum dot according to any one of claims 1 to 4, comprising the steps of,

6. The method for preparing the ultraviolet and blue light resistant carbon quantum dot according to claim 5, wherein the method comprises the following steps: in the step S2, the mixed solution was filtered through a 0.22 μm microfiltration membrane.

7. The method for preparing the ultraviolet and blue light resistant carbon quantum dot according to claim 5, wherein the method comprises the following steps: in the S4, the turbid solution is centrifuged to collect a yellow precipitate.

8. The method for preparing the ultraviolet and blue light resistant carbon quantum dot according to claim 5, wherein the method comprises the following steps: and in the S4, washing the yellow precipitate for 2-3 times by using deionized water, and drying the washed yellow precipitate in a freeze dryer to obtain dried yellow powder.

9. The method for preparing the ultraviolet and blue light resistant carbon quantum dot according to claim 5, wherein the method comprises the following steps: and in the step S1, carrying out ultrasonic treatment on the solution in which the ultraviolet absorbent and the nitrogenous organic matters are dissolved for 2-10 min to obtain a mixed solution.

10. The application of the carbon quantum dots is characterized in that: the application of the carbon quantum dots as recited in any one of claims 1 to 4 in manufacturing ultraviolet-proof and blue-light-proof products.