Preparation of Bacteriostatic Graphene Quantum Dots and Their Application in Washing and Care Products

Abstract

The present invention belongs to the field of graphene products, and specifically relates to a preparation process of antibacterial graphene quantum dots, particularly to the preparation of antibacterial graphene quantum dots and their application in washing and care products. As a novel carbon-based nanomaterial, graphene quantum dots have great potential in the antibacterial field due to their unique properties. The outstanding advantages in biocompatibility, mature preparation technology and rich sources also facilitate their application in the antibacterial field. Therefore, the present invention prepares F- and B-doped graphene quantum dots, which have good stability, excellent solubility and high biocompatibility. In addition, a mixed extract is extracted from plants, and a hair conditioner containing antibacterial graphene quantum dots is prepared, achieving unexpected technical effects.

Description

Technical Field

[0001] The present invention belongs to the field of graphene products, and particularly relates to a preparation process of antibacterial graphene quantum dots, and more particularly to the preparation of antibacterial graphene quantum dots and their application in washing and care products. Background Art

[0002] Major diseases and deaths induced by pathogenic microorganism infections have always threatened human health and safety. According to statistics, nearly 20 million people die each year due to pathogenic microorganism infections. In clinical treatment, the problem of pathogenic microorganism drug resistance is becoming increasingly serious. Drug-resistant bacteria can transfer drug-resistant genes to other bacteria through horizontal gene transfer, further leading to the emergence of multi-drug resistance. However, when new antibiotics are developed, bacteria will quickly develop resistance to them, which makes people on the verge of facing a situation where there are no drugs available. At the same time, biofilms are another important cause of drug resistance. Biofilms can adhere to the surfaces of living tissues, surgical instruments, and medical implants, making them difficult to detect and completely remove, thus easily causing the persistence and recurrence of infections, which poses a further challenge to the treatment of pathogenic microorganism infections. Therefore, there is an urgent need to explore and develop new antibacterial agents to combat pathogenic bacteria, especially multi-drug resistant microorganisms. Nano-antibacterial materials are a class of new materials with antibacterial properties. Due to the special properties of nano-antibacterial agents such as high reaction activity and high specific surface area, the antibacterial effect is greatly improved. Compared with traditional antibiotics, nano-antibacterial materials often inhibit or kill bacteria in multiple ways and are not easily induced to develop drug resistance in bacteria. In recent years, nano-antibacterial materials have gradually become a new type of antibacterial substance widely concerned in the academic community.

[0003] Carbon atoms combine with each other in various ways to form different carbon allotropes, generating various carbon-based nano antibacterial materials, including zero-dimensional fullerenes, nanodiamonds, carbon dots, graphene quantum dots, one-dimensional carbon nanotubes, two-dimensional graphene and its derivatives, and graphitic carbon nitride. Due to their unique physical and chemical properties, high environmental friendliness and biocompatibility, carbon nanomaterials have outstanding advantages in antibacterial aspects. In addition to directly causing damage to bacterial cells, graphene has a large surface area and can inhibit the normal metabolism and growth of bacteria by wrapping bacterial cells and isolating them from nutrients. When its concentration is relatively high, it will also cause irreversible damage to the bacterial cell membrane and leakage of cytoplasm, resulting in bacterial death. Although graphene-based materials have great application potential in water disinfection, wound dressings, antibacterial coatings for medical devices, and even as antibacterial drugs, there are still certain limitations in practical applications. Impurities present in the synthesis may have an adverse impact on their antibacterial properties to a certain extent. Since the discovery of graphene, its unique optical properties, excellent chemical stability and good biocompatibility have attracted great attention from researchers in various fields. The development of graphene quantum dots has further promoted the entry of graphene-based materials into the biomedical field. Therefore, the present invention designs a preparation process of antibacterial graphene quantum dots, and in particular, its application in washing and care products is of great significance for promoting social development. Summary of the Invention

[0004] In order to overcome the deficiencies of the prior art, the object of the present invention is to provide a preparation process of antibacterial graphene quantum dots, specifically related to the preparation of antibacterial graphene quantum dots and their application in washing and care products. The present invention is achieved through the following technical solutions:

[0005] S1. Add 5-7 g of coronene to 30-50 ml of concentrated nitric acid, keep warm at 55-60 °C for 4-6 h to synthesize nitrocoronene, centrifuge to remove excess nitric acid, and then wash it with N,N-dimethylformamide (DMF) 3-5 times.

[0006] S2. Take 2 - 3 g of the nitrocoronene prepared in step S1, 0.4 - 0.6 g of ammonium fluoride, and 0.5 - 0.8 g of boric acid and place them in a 100 mL microwave reaction kettle. Then add 35 - 45 mL of polyethyleneimine and 12 - 15 mL of N,N - dimethylformamide (DMF). After stirring evenly, put the microwave reaction kettle into the reactor. Set the microwave power to 300 - 600 W, control the microwave reaction temperature at 220 - 260 °C, and the microwave reaction time to 2 - 3 h. The addition of ammonium fluoride and boric acid in this step can obtain F and B - doped graphene quantum dots. Under the action of microwave heating, nitrocoronene and polyethyleneimine can be used to prepare graphene quantum dots. Microwave heating has the characteristics of instantaneity and rapidity, and can prepare smaller materials, which is beneficial to the synthesis of graphene quantum dots. There is a synergistic effect between F and B, and the two together change the electronic structure around the graphene quantum dots, enabling them to better combine with other nanoparticles.

[0007] S3. Weigh 0.5 - 0.7 g of 2 - aminoterephthalic acid and place it in a 100 mL polytetrafluoroethylene reaction kettle. Measure 13 - 17 mL of DMF and 13 - 21 mL of anhydrous methanol and add them to the above - mentioned reaction kettle. Then quickly add 0.8 - 1.1 mL of tetra - isopropyl titanate and 0.5 g of copper nitrate to the reaction kettle and stir it evenly. Put the polytetrafluoroethylene reaction kettle into the stainless - steel kettle jacket, and then place it in an electro - thermal constant - temperature forced - air drying oven. Heat - treat it at 180 - 200 °C for 12 - 16 h. After the reaction is completed, wait for the reaction kettle to cool to room temperature, centrifuge to remove the supernatant, wash the yellow precipitate 3 - 5 times with anhydrous DMF and anhydrous methanol respectively, centrifuge to remove the DMF and methanol solutions, collect the yellow precipitate, and vacuum - dry it at 80 °C for 12 h to obtain the metal - organic framework of nano - polyhedron Ti - Cu.

[0008] S4. Weigh 0.4 - 0.5 g of the metal - organic framework of Ti - Cu prepared in step S3 and spread it flat in a ceramic boat. Place the ceramic boat in the middle part of the quartz tube of the tube furnace. In an air atmosphere, set the tube furnace to heat up to 750 °C at a heating rate of 5 °C / min and keep it warm for 2 - 3 h. After natural cooling, Ti / Cu - O x can be obtained. This step converts the metal - organic framework of Ti - Cu into Ti / Cu - O x , which can combine the advantages of MOF and oxides. Combining Ti / Cu - O x with the F and B - doped graphene quantum dots prepared in step S2 can better play an antibacterial role and help improve the cleaning effect. In addition, the specific surface area of Ti / Cu - Ox prepared using the metal - organic framework of Ti - Cu is relatively large, and it can adsorb dirt well.

[0009] S5. Heat 220 - 260 mL of deionized water to 58 °C, and successively add 20 - 25 ml of glycerol, 1.2 - 1.8 g of cetyltrimethylammonium bromide (CTAB), 1.1 - 2.6 g of F, B-doped graphene quantum dots prepared in step S2, and 0.3 - 0.5 g of Ti / Cu-O prepared in step S4 at this temperature. x , when the temperature drops to 28 °C, add 15 - 20 g of sodium carboxymethyl cellulose and 5 g of sodium dodecyl sulfate (SDS), then add 50 - 80 mL of plant extract while stirring, and finally adjust the pH to 6.9 - 7.3 with a trisodium citrate aqueous solution to prepare a hair conditioner containing antibacterial graphene quantum dots. In this step, Ti / Cu-O x can be tightly combined with graphene quantum dots through π-π interaction, and the F, B-doped graphene quantum dots are negatively charged around, and can attract metal ions through electrostatic interaction. This graphene quantum dot also has a good antibacterial effect. Combine Ti / Cu-O x with graphene quantum dots, and the attraction between them can thermodynamically weaken the tendency of material aggregation, which is beneficial to improving the antibacterial activity of the material. In addition, graphene quantum dots and Ti / Cu-O x complement each other, cooperate with the plant extract, can play a good antibacterial and cleaning effect, and the high specific surface area is conducive to adsorbing dirt.

[0010] Preferably: In step S1 of the present invention, 5 g of coronene is added to 30 ml of concentrated nitric acid, and kept warm at 55 °C for 4 h to synthesize nitrocoronene. Centrifuge to remove excess nitric acid, and then wash 5 times with N,N-dimethylformamide (DMF).

[0011] Preferably: In step S2 of the present invention, take 3 g of nitrocoronene prepared in step S1, 0.4 g of ammonium fluoride, and 0.8 g of boric acid and place them in a 100 mL microwave reaction kettle. Then add 45 mL of polyethyleneimine and 12 mL of N,N-dimethylformamide (DMF), stir evenly, and put the microwave reaction kettle into the reactor; set the microwave power to 300 W, control the microwave reaction temperature at 220 °C, and the microwave reaction time is 3 h; the addition of ammonium fluoride and boric acid in this step can obtain F, B-doped graphene quantum dots. Under the action of microwave heating, nitrocoronene and polyethyleneimine can be used to prepare graphene quantum dots. Microwave heating has the characteristics of instantaneous and rapid, and can prepare smaller materials, which is beneficial to the synthesis of graphene quantum dots. There is a synergistic effect between F and B, and the two jointly change the electronic structure around the graphene quantum dot, making it better able to combine with other nanoparticles.

[0012] Preferably: In step S2 of the present invention, 2 g of the nitrocoronene prepared in step S1, 0.4 g of ammonium fluoride, and 0.5 g of boric acid are placed in a 100 mL microwave reaction kettle. Then, 35 mL of polyethyleneimine and 12 mL of N,N-dimethylformamide (DMF) are added. After stirring evenly, the microwave reaction kettle is placed in a reactor; the microwave power is set to 600 W, the microwave reaction temperature is controlled at 260 °C, and the microwave reaction time is 3 h; the addition of ammonium fluoride and boric acid in this step can obtain F- and B-doped graphene quantum dots. Under the action of microwave heating, nitrocoronene and polyethyleneimine can be used to prepare graphene quantum dots. Microwave heating has the characteristics of being instantaneous and rapid, and can prepare smaller materials, which is beneficial to the synthesis of graphene quantum dots. There is a synergistic effect between F and B, and the two jointly change the electronic structure around the graphene quantum dots, enabling them to better combine with other nanoparticles.

[0013] Preferably: In step S3 of the present invention, 0.7 g of 2-aminoterephthalic acid is weighed into a 100 mL polytetrafluoroethylene reaction kettle. 17 mL of DMF and 13 mL of anhydrous methanol are measured and added to the above reaction kettle. Then, 1.1 mL of titanium tetraisopropoxide and 0.5 g of copper nitrate are quickly added to the reaction kettle and stirred evenly. The polytetrafluoroethylene reaction kettle is placed in a stainless steel kettle jacket, and then put into an electrothermal constant temperature blast drying oven for heat treatment at 180 °C for 16 h. After the reaction is completed, wait for the reaction kettle to cool to room temperature, centrifuge to remove the supernatant, wash the yellow precipitate 5 times with anhydrous DMF and anhydrous methanol respectively, centrifuge to remove the DMF and methanol solutions, collect the yellow precipitate, and vacuum dry it at 80 °C for 12 h to obtain the metal-organic framework of nano polyhedron Ti-Cu.

[0014] Preferably: In step S4 of the present invention, 0.5 g of the metal-organic framework of Ti-Cu prepared in step S3 is spread out flat in a ceramic boat. The ceramic boat is placed in the middle part of the quartz tube of a tube furnace. In an air atmosphere, the tube furnace is set to heat up to 750 °C at a heating rate of 5 °C / min and keep it warm for 3 h. After natural cooling, Ti / Cu-O can be obtained. x This step converts the metal-organic framework of Ti-Cu into Ti / Cu-O. x It can combine the advantages of MOF and the advantages of oxides. Combining Ti / Cu-O x with the F- and B-doped graphene quantum dots prepared in step S2 can better play an antibacterial role and help improve the cleaning effect. In addition, the specific surface area of Ti / Cu-O x prepared from the metal-organic framework of Ti-Cu is relatively large, and it can adsorb dirt well.

[0015] Preferably: In step S4 of the present invention, 0.4 g of the metal-organic framework of Ti-Cu prepared in step S3 is weighed and laid flat in a ceramic boat. The ceramic boat is placed in the middle part of the quartz tube of a tube furnace. Under an air atmosphere, the tube furnace is set to be heated at a heating rate of 5 °C / min to 750 °C and kept warm for 3 h. After natural cooling, Ti / Cu-O can be obtained. x This step converts the metal-organic framework of Ti-Cu into Ti / Cu-O. x It can combine the advantages of MOF with those of oxides. Combining Ti / Cu-O x with the F, B-doped graphene quantum dots prepared in step S2 can better play an antibacterial role and help improve the cleaning efficacy. In addition, the Ti / Cu-O x prepared from the metal-organic framework of Ti-Cu has a relatively large specific surface area and can well adsorb dirt.

[0016] Preferably: In step S5 of the present invention, 220 mL of deionized water is heated to 58 °C. At this temperature, 25 ml of glycerol, 1.2 g of cetyltrimethylammonium bromide (CTAB), 2.6 g of the F, B-doped graphene quantum dots prepared in step S2, and 0.3 g of Ti / Cu-O prepared in step S4 are added in sequence. x When the temperature drops to 28 °C, 20 g of sodium carboxymethyl cellulose and 5 g of sodium dodecyl sulfate (SDS) are added. Then, 50 - 80 mL of plant extract is added while stirring. Finally, the pH is adjusted to 7.3 with a trisodium citrate aqueous solution, and a hair conditioner containing antibacterial graphene quantum dots can be prepared. In this step, Ti / Cu-O x can be tightly combined with graphene quantum dots through π-π interaction, and the F, B-doped graphene quantum dots are negatively charged around and can attract metal ions through electrostatic interaction. Combining Ti / Cu-O x with graphene quantum dots, the attraction between them can thermodynamically weaken the tendency of material aggregation and is beneficial to enhancing the antibacterial activity of the material. In addition, graphene quantum dots and Ti / Cu-O x complement each other and, combined with the plant extract, can well play an antibacterial and cleaning effect, and the high specific surface area is beneficial to adsorbing dirt.

[0017] Preferably: the method for preparing the plant extract described in S5 of the present invention is specifically as follows: weigh 26 g of jasmine, 31 g of green tea, 6 g of mint leaves and 10 g of ginger, mix them evenly, grind and mash them, add 250 mL of deionized water, decoct them 10 times, each time for 30 min, combine the filtrate, and obtain the plant extract by distillation. In the mixed extract prepared in this step, natural herbs such as jasmine, green tea, mint leaves and ginger complement each other and have a certain inhibitory effect on different bacteria. Using it in a washing liquid can better enhance the antibacterial effect.

[0018] Preferably: the peptone, yeast powder and agar described in the present invention are purchased from Shanghai Microbiology Technology Co., Ltd.

[0019] Preferably: the coronene of the present invention is purchased from Sigma-Aldrich Company, the concentrated nitric acid is purchased from Shanghai Sinopharm Chemical Reagent Co., Ltd.; and the polyethyleneimine is purchased from Aladdin Chemical Reagent Company.

[0020] Preferably: the Escherichia coli described in the present invention is purchased from Shanghai Collection Biotechnology Center.

[0021] Preferably, the anhydrous ethanol, sterile physiological saline, hydrochloric acid, sodium hydroxide, PBS, 2.5% glutaraldehyde and other reagents described in the present invention are purchased from Woridas Co., Ltd.

[0022] The invention is beneficial in that:

[0023] 1. The synthesis process of the present invention has the advantages of simple operation, fast reaction speed, green environmental protection, and high yield.

[0024] 2. Ti / Cu-O prepared by the present invention x It can be tightly combined with graphene quantum dots through π-π interaction, and the graphene quantum dots doped with F and B have negative charges around them, which can attract metal ions through electrostatic interaction. x When combined with graphene quantum dots, the attraction between them can thermodynamically weaken the tendency of material aggregation, which is beneficial to improving the antibacterial activity of the material.

[0025] 3. The F and B doped graphene quantum dots prepared by the present invention have broader prospects in the application of biomedicine than other nano antibacterial materials.

[0026] 4. The F and B doped graphene quantum dots prepared by the present invention have good stability, excellent solubility and high biocompatibility.

[0027] 5. There is a synergistic effect between F and B in the F-doped graphene quantum dots prepared by the present invention, and the two together change the electronic structure around the graphene quantum dots, so that they can better combine with other nanoparticles. Description of the Drawings

[0028] Figure 1 It is a graph showing the effect of graphene quantum dots prepared in Example 1, Example 2 and Comparative Example 1-4 of the present invention on the growth curve of Escherichia coli.

[0029] Figure 2 It is a surface scanning energy spectrum diagram of F, B-doped graphene quantum dots prepared in Example 3 of the present invention.

[0030] Figure 3 It is a spherical aberration electron microscope transmission diagram of F, B-doped graphene quantum dots prepared in Example 3 of the present invention. Detailed Embodiments

[0031] The following specific examples illustrate the embodiments of the present invention. Those skilled in the art can easily understand other advantages and effects of the present invention from the content disclosed in this specification. The present invention can also be implemented or applied through other different specific embodiments. Various details in this specification can also be modified or changed based on different viewpoints and applications without departing from the spirit of the present invention. It should be noted that, without conflict, the following embodiments and the features in the embodiments can be combined with each other.

[0032] Example 1

[0033] S1. Add 5 g of coronene to 30 ml of concentrated nitric acid, keep it warm at 55 °C for 4 h to synthesize nitrocoronene, centrifuge to remove excess nitric acid, and then wash it 3 times with N,N-dimethylformamide (DMF).

[0034] S2. Take 2 g of the nitrocoronene prepared in step S1, 0.4 g of ammonium fluoride and 0.5 g of boric acid and place them in a 100 mL microwave reaction kettle. Then add 35 mL of polyethyleneimine and 12 mL of N,N-dimethylformamide (DMF), stir evenly, and put the microwave reaction kettle into the reactor; set the microwave power to 300 W, control the microwave reaction temperature at 220 °C, and the microwave reaction time is 2 h; the addition of ammonium fluoride and boric acid in this step can obtain F, B-doped graphene quantum dots. Under the action of microwave heating, nitrocoronene and polyethyleneimine can be used to prepare graphene quantum dots. Microwave heating has the characteristics of instantaneity and rapidity, and can prepare smaller materials, which is beneficial to the synthesis of graphene quantum dots. There is a synergistic effect between F and B, and the two jointly change the electronic structure around the graphene quantum dots, enabling them to better combine with other nanoparticles.

[0035] S3. Weigh 0.5 g of 2-aminoterephthalic acid into a 100 mL polytetrafluoroethylene reaction kettle. Measure 13 mL of DMF and 13 mL of anhydrous methanol and add them into the above reaction kettle. Then quickly add 0.8 mL of titanium tetraisopropoxide and 0.5 g of copper nitrate into the reaction kettle and stir them evenly. Place the polytetrafluoroethylene reaction kettle into a stainless-steel kettle jacket, and then put it into an electrothermal constant-temperature forced-air drying oven. Heat-treat it at 180 °C for 12 h. After the reaction is completed, wait for the reaction kettle to cool to room temperature, centrifuge to remove the supernatant, wash the yellow precipitate 3 - 5 times with anhydrous DMF and anhydrous methanol respectively, centrifuge to remove the DMF and methanol solutions, collect the yellow precipitate, and vacuum-dry it at 80 °C for 12 h to obtain the metal-organic framework of nano polyhedron Ti-Cu.

[0036] S4. Weigh 0.4 g of the metal-organic framework of Ti-Cu prepared in step S3 and spread it flat in a ceramic boat. Place the ceramic boat in the middle part of the quartz tube of a tube furnace. Under an air atmosphere, set the tube furnace to heat up to 750 °C at a heating rate of 5 °C / min and keep it warm for 2 h. After natural cooling and temperature reduction, Ti / Cu-O can be obtained. x . This step converts the metal-organic framework of Ti-Cu into Ti / Cu-O. x , which can combine the advantages of MOF and oxides. Combining Ti / Cu-O x with the F, B-doped graphene quantum dots prepared in step S2 can better play an antibacterial role and help improve the cleaning efficacy. In addition, the specific surface area of Ti / Cu-O x prepared from the metal-organic framework of Ti-Cu is relatively large, and it can adsorb dirt well.

[0037] S5. Weigh 26 g of jasmine flowers, 31 g of green tea, 6 g of mint leaves and 10 g of ginger, mix them evenly, grind and crush them, then add 250 mL of deionized water, decoct for 10 times, 30 min each time, combine the filtrates, and obtain the plant extract by distillation. In the mixed extract prepared in this step, natural herbs such as jasmine flowers, green tea, mint leaves and ginger complement each other and have a certain inhibitory effect on different bacteria. Using it in the washing liquid can better enhance the antibacterial effect.

[0038] S6. Heat 220 mL of deionized water to 58 °C, and at this temperature, add 20 ml of glycerol, 1.2 g of cetyltrimethylammonium bromide (CTAB), 1.1 g of the F, B-doped graphene quantum dots prepared in step S2 and 0.3 g of Ti / Cu-O prepared in step S4 in sequence. x, when the temperature drops to 28 °C, add 15 g of sodium carboxymethyl cellulose and 5 g of sodium dodecyl sulfate (SDS), then add 50 mL of the plant extract prepared in step S5 while stirring, and finally adjust the pH to 6.9 with a trisodium citrate aqueous solution to obtain a hair conditioner containing antibacterial graphene quantum dots. In this step, Ti / Cu-O x can be tightly bound to graphene quantum dots through π-π interactions, while the negatively charged F- and B-doped graphene quantum dots can attract metal ions through electrostatic interactions. Combine Ti / Cu-O x with graphene quantum dots, and the attraction between them can thermodynamically weaken the tendency of material aggregation, which is beneficial to improving the antibacterial activity of the material. In addition, graphene quantum dots and Ti / Cu-O x complement each other and cooperate with the plant extract to achieve a good antibacterial and cleaning effect, and the high specific surface area is conducive to adsorbing dirt.

[0039] Comparative Example 1: Except that 0.4 g of ammonium fluoride is not added in step S2, the other steps are the same as those in Example 1.

[0040] Comparative Example 2: Except that 0.5 g of boric acid is not added in step S2, the other steps are the same as those in Example 1.

[0041] Comparative Example 3: Except that 0.4 g of ammonium fluoride and 0.5 g of boric acid are not added in step S2, the other steps are the same as those in Example 1.

[0042] Preparation of bacterial liquid and culture medium in the present invention: Dissolve 1 g of tryptone, 0.45 g of sodium chloride and yeast extract in 100 mL of deionized water, sterilize at 120 °C for 30 min and then cool to room temperature to obtain an agar liquid medium. The agar solid medium needs to add 4 g of agar to the above formula, pour it into a sterilized petri dish after autoclaving, wait for the agar to solidify, and store it at 4 °C for later use. Take an appropriate amount of Escherichia coli bacterial liquid and add it to 32 mL of the agar liquid medium, and at 37 °C, at a rotation speed of 220 r·min -1After overnight incubation on a shaker, 10 mL of the bacterial solution was centrifuged, and the absorbance A of the bacterial solution was adjusted to 0.5 to obtain an Escherichia coli bacterial solution. In 5 newly sterilized culture flasks, 60 mL of agar liquid medium, 200 μL of the Escherichia coli solution treated by ultraviolet irradiation for 20 min, and the graphene quantum dots prepared in Example 1 and Comparative Examples 1-3 of the present invention were added, and their concentration was adjusted to 0.9 mg / mL, and the mixture was cultured with shaking at 37 °C and 220 r / min. The absorbance A at 600 nm of the solution was recorded every 1 h until the absorbance value of the bacterial solution no longer increased significantly. Each group of experiments was repeated 3 times. The initial absorbance of the bacterial solution was the same. As the culture time increased, Escherichia coli grew and reproduced continuously in the medium, and the absorbance of the solution increased continuously. Figure 1 It is a graph showing the effect of the graphene quantum dots prepared in Example 1, 2 and Comparative Examples 1-4 of the present invention on the growth curve of Escherichia coli. It can be seen from the graph that the inhibitory effect of the graphene quantum dots prepared in Comparative Examples 3 and 4 on Escherichia coli is not ideal. When the graphene quantum dots prepared in Comparative Examples 1 and 2 are added, the absorbance of the solution decreases, and the antibacterial effect gradually increases. After the graphene quantum dots prepared in Examples 1 and 2 of the present invention are added, the growth curve of Escherichia coli is almost parallel to the horizontal axis, indicating that the content of the bacterial solution in the solution is extremely low, and the growth of Escherichia coli is almost completely inhibited. It can be seen that the present invention uses microwave heating, which has the characteristics of instantaneous and rapid, and synthesizes F, B-doped graphene quantum dots. There is a synergistic effect between F and B, and the two jointly change the electronic structure around the graphene quantum dots, improving their antibacterial effect. In Comparative Example 3, the graphene quantum dots are not modified with F and B, and in Comparative Example 4, no Cu element is added, and Ti / Cu-O cannot be prepared x resulting in poor antibacterial effect, which indirectly shows that Ti / Cu-O in the present invention x can be tightly combined with graphene quantum dots through π-π interaction, and the F, B-doped graphene quantum dots are negatively charged around, and can attract metal ions through electrostatic interaction. Combining Ti / Cu-O x with graphene quantum dots, the attraction between each other can thermodynamically weaken the tendency of material aggregation, which is beneficial to improving the antibacterial activity of the material.

[0043] Example 2

[0044] S1. Add 7 g of coronene to 50 mL of concentrated nitric acid, keep it warm at 60 °C for 6 h to synthesize nitrocoronene, centrifuge to remove excess nitric acid, and then wash it 5 times with N,N-dimethylformamide (DMF).

[0045] S2. Take 3 g of the nitrocoronene prepared in step S1, 0.6 g of ammonium fluoride, and 0.8 g of boric acid and place them in a 100 mL microwave reactor. Then add 45 mL of polyethyleneimine and 15 mL of N,N-dimethylformamide (DMF). After stirring evenly, place the microwave reactor into the reactor. Set the microwave power to 600 W, control the microwave reaction temperature at 260 °C, and the microwave reaction time to 3 h. The addition of ammonium fluoride and boric acid in this step can obtain F and B co-doped graphene quantum dots. Under the action of microwave heating, nitrocoronene and polyethyleneimine can be used to prepare graphene quantum dots. Microwave heating has the characteristics of instantaneity and rapidity, and can prepare smaller materials, which is beneficial to the synthesis of graphene quantum dots. There is a synergistic effect between F and B, and the two jointly change the electronic structure around the graphene quantum dots, enabling them to better combine with other nanoparticles.

[0046] S3. Weigh 0.7 g of 2-aminoterephthalic acid and place it in a 100 mL polytetrafluoroethylene reactor. Measure 17 mL of DMF and 21 mL of anhydrous methanol and add them to the above reactor. Then quickly add 1.1 mL of titanium tetraisopropoxide and 0.5 g of copper nitrate to the reactor and stir evenly. Place the polytetrafluoroethylene reactor into a stainless steel reactor jacket, and then put it into an electrothermal constant temperature blast drying oven. Heat-treat it at 200 °C for 16 h. After the reaction is completed, wait for the reactor to cool to room temperature, centrifuge to remove the supernatant, wash the yellow precipitate 3 - 5 times with anhydrous DMF and anhydrous methanol respectively, centrifuge to remove the DMF and methanol solutions, collect the yellow precipitate, and vacuum dry it at 80 °C for 12 h to obtain the metal-organic framework of nano-polyhedron Ti-Cu.

[0047] S4. Weigh 0.5 g of the metal-organic framework of Ti-Cu prepared in step S3 and spread it flat in a ceramic boat. Place the ceramic boat in the middle part of the quartz tube of a tube furnace. In an air atmosphere, set the tube furnace to heat up to 750 °C at a heating rate of 5 °C / min and keep it warm for 3 h. After natural cooling and temperature reduction, Ti / Cu-O can be obtained. x This step converts the metal-organic framework of Ti-Cu into Ti / Cu-O. x It can combine the advantages of MOF with those of oxides. Combining Ti / Cu-O x with the F and B co-doped graphene quantum dots prepared in step S2 can better play an antibacterial role and help improve the cleaning effect. In addition, the specific surface area of Ti / Cu-O x prepared using the metal-organic framework of Ti-Cu is relatively large, and it can well adsorb dirt.

[0048] S5. Weigh 26 g of jasmine flowers, 31 g of green tea, 6 g of mint leaves and 10 g of ginger, mix them evenly, grind and mash them, then add 250 mL of deionized water, and decoct for 10 times, 30 minutes each time. Combine the filtrates and obtain the plant extract by distillation. In the mixed extract prepared in this step, natural herbs such as jasmine flowers, green tea, mint leaves and ginger complement each other and have a certain inhibitory effect on different bacteria. Using it in the washing liquid can better enhance the antibacterial effect.

[0049] S6. Heat 260 mL of deionized water to 58 °C, and successively add 25 ml of glycerol, 1.8 g of cetyltrimethylammonium bromide (CTAB), 2.6 g of the F, B-doped graphene quantum dots prepared in step S2, and 0.5 g of Ti / Cu-O prepared in step S4 x , when the temperature drops to 28 °C, add 20 g of sodium carboxymethyl cellulose and 5 g of sodium dodecyl sulfate (SDS), then add 80 mL of the plant extract prepared in step S5 while stirring, and finally adjust the pH to 7.3 with a trisodium citrate aqueous solution to prepare a hair conditioner containing antibacterial graphene quantum dots. In this step, Ti / Cu-O x can be tightly combined with graphene quantum dots through π-π interaction, and the F, B-doped graphene quantum dots are negatively charged around and can attract metal ions through electrostatic interaction. Combine Ti / Cu-O x with graphene quantum dots, and the attraction between them can thermodynamically weaken the tendency of material aggregation, which is beneficial to improving the antibacterial activity of the material. In addition, graphene quantum dots and Ti / Cu-O x complement each other, cooperate with the plant extract, can play a good antibacterial and cleaning effect, and the high specific surface area is conducive to adsorbing dirt.

[0050] Comparative Example 4: In step S3, except for not adding 0.5 g of copper nitrate, the other steps are the same as those in Example 2.

[0051] Comparative Example 5: In step S3, except for not adding 1.1 mL of titanium isopropoxide, the other steps are the same as those in Example 2.

[0052] Take 0.2 mL of the above-mentioned Escherichia coli solution into 5 2-mL glass tubes, and add 0.5 mL of the hair conditioners prepared in Example 2 and Comparative Examples 4 and 5 and 1 mL of deionized water respectively. Irradiate with a near-infrared laser at a position 5 cm directly above the tube wall for 20 minutes, and the bacterial solution without adding the hair conditioner is used as an experimental control. Dilute the bacterial solution by 10 4Multiply, take 100 μL and drop it on the agar solid medium. Use a spreader to evenly spread the bacterial solution on the plate, and incubate it in a constant temperature incubator at 37 °C for 24 h and then count. The survival rate of Escherichia coli is calculated according to the following formula: Bacterial survival rate = number of colonies in the experimental group / number of colonies in the control group * 100%. After repeating each group of data 5 times, take the average value and calculate the error.

[0053] Table 1. Survival rate of Escherichia coli

[0054]

[0055] The experimental results described in Table 1 show that the F, B-doped graphene quantum prepared by the present invention can inhibit the growth of Escherichia coli. There is a certain synergistic effect between Cu and Ti in Ti / Cu-O x In Comparative Examples 4 and 5, it shows that no matter which metal, Cu or Ti, is lacking, the antibacterial effect of the hair conditioner will be greatly reduced. In the present invention, Ti / Cu-O x can be tightly combined with graphene quantum dots through π-π interaction, and the F, B-doped graphene quantum dots are negatively charged around, and can attract metal ions through electrostatic interaction. Combining Ti / Cu-O x with graphene quantum dots, the attraction between each other can thermodynamically weaken the tendency of material aggregation, which is beneficial to improving the antibacterial activity of the material. In addition, graphene quantum dots and Ti / Cu-O x complement each other and cooperate with plant extracts, which can play a good antibacterial and cleaning effect, and the high specific surface area is conducive to adsorbing dirt. It can be seen that in the antibacterial process of the F, B-doped graphene quantum prepared by the present invention, its own structure can also damage the cell membrane of Escherichia coli, and has broad development prospects in antibacterial.

[0056] Example 3

[0057] S1. Add 5-7 g of coronene to 35 ml of concentrated nitric acid, keep it warm at 56 °C for 5 h to synthesize nitrocoronene, centrifuge to remove excess nitric acid, and then wash it 4 times with N,N-dimethylformamide (DMF).

[0058] S2. Take 2.5 g of the nitrocoronene prepared in step S1, 0.55 g of ammonium fluoride, and 0.7 g of boric acid and place them in a 100 mL microwave reaction kettle. Then add 44 mL of polyethyleneimine and 14 mL of N,N-dimethylformamide (DMF). After stirring evenly, put the microwave reaction kettle into the reactor. Set the microwave power to 400 W, control the microwave reaction temperature at 240 °C, and the microwave reaction time to 2.6 h. The addition of ammonium fluoride and boric acid in this step can obtain F and B co-doped graphene quantum dots. Under the action of microwave heating, nitrocoronene and polyethyleneimine can be used to prepare graphene quantum dots. Microwave heating has the characteristics of instantaneity and rapidity, and can prepare smaller materials, which is beneficial to the synthesis of graphene quantum dots. There is a synergistic effect between F and B, and the two jointly change the electronic structure around the graphene quantum dots, enabling them to better combine with other nanoparticles.

[0059] S3. Weigh 0.6 g of 2-aminoterephthalic acid and place it in a 100 mL polytetrafluoroethylene reaction kettle. Measure 16 mL of DMF and 17 mL of anhydrous methanol and add them to the above reaction kettle. Then quickly add 0.9 mL of titanium tetraisopropoxide and 0.5 g of copper nitrate to the reaction kettle and stir evenly. Put the polytetrafluoroethylene reaction kettle into a stainless steel kettle sleeve, and then place it in an electrothermal constant temperature blast drying oven. Heat-treat it at 190 °C for 15 h. After the reaction is completed, wait for the reaction kettle to cool to room temperature, centrifuge to remove the supernatant, wash the yellow precipitate 4 times with anhydrous DMF and anhydrous methanol respectively, centrifuge to remove the DMF and methanol solutions, collect the yellow precipitate, and vacuum dry it at 80 °C for 12 h to obtain the metal-organic framework of nano-polyhedron Ti-Cu.

[0060] S4. Weigh 0.45 g of the metal-organic framework of Ti-Cu prepared in step S3 and spread it flat in a ceramic boat. Place the ceramic boat in the middle part of the quartz tube of the tube furnace. In an air atmosphere, set the tube furnace to heat up to 750 °C at a heating rate of 5 °C / min and keep it warm for 2.6 h. After natural cooling, Ti / Cu-O can be obtained. x This step converts the metal-organic framework of Ti-Cu into Ti / Cu-O. x It can combine the advantages of MOF and oxides. Combining Ti / Cu-O x with the F and B co-doped graphene quantum dots prepared in step S2 can better play an antibacterial role and help improve the cleaning effect. In addition, the specific surface area of Ti / Cu-O x prepared using the metal-organic framework of Ti-Cu is relatively large, and it can well adsorb the dirt on the surface.

[0061] S5. Weigh 26 g of jasmine flowers, 31 g of green tea, 6 g of mint leaves and 10 g of ginger, mix them evenly, grind and mash them, then add 250 mL of deionized water, boil for 10 times, 30 minutes each time, combine the filtrates, and obtain the plant extract by distillation. In the mixed extract prepared in this step, natural herbs such as jasmine flowers, green tea, mint leaves and ginger complement each other and have a certain inhibitory effect on different bacteria. Using it in the washing liquid can better enhance the antibacterial effect.

[0062] S6. Heat 240 mL of deionized water to 58 °C, and successively add 24 ml of glycerol, 1.4 g of cetyltrimethylammonium bromide (CTAB), 2.4 g of the F, B-doped graphene quantum dots prepared in step S2, and 0.4 g of Ti / Cu-O prepared in step S4 x , when the temperature drops to 28 °C, add 19 g of sodium carboxymethyl cellulose and 5 g of sodium dodecyl sulfate (SDS), then add 70 mL of the plant extract prepared in step S5 while stirring, and finally adjust the pH to 7.0 with a trisodium citrate aqueous solution to prepare a hair conditioner containing antibacterial graphene quantum dots. In this step, Ti / Cu-O x can be tightly combined with graphene quantum dots through π-π interactions, and the F, B-doped graphene quantum dots are negatively charged around and can attract metal ions through electrostatic interactions. Combine Ti / Cu-O x with graphene quantum dots, and the attraction between them can thermodynamically weaken the tendency of material aggregation, which is beneficial to improving the antibacterial activity of the material. In addition, graphene quantum dots and Ti / Cu-O x complement each other and cooperate with the plant extract, which can well achieve the antibacterial and cleaning effects, and the high specific surface area is conducive to adsorbing dirt, and can better achieve the cleaning purpose.

[0063] Figure 2 is the surface scanning energy spectrum diagram of the F, B-doped graphene quantum dots prepared in Example 3 of the present invention. It can be seen from the energy spectrum that the elements C, N, F, and B are evenly distributed on the surface of graphene. Figure 3 is the spherical aberration electron microscope transmission diagram of the F, B-doped graphene quantum dots prepared in Example 3 of the present invention. It can be seen from the figure that the bright spots are the quantum dots of graphene. It is proved that the process route of the present invention successfully synthesizes F, B-doped graphene quantum dots.

[0064] Example 4

[0065] S1. Add 5.6 g of coronene to 46 mL of concentrated nitric acid, keep warm at 58 °C for 5 h to synthesize nitrocoronene, centrifuge to remove excess nitric acid, and then wash 4 times with N,N-dimethylformamide DMF.

[0066] S2. Take 2 g of the nitrocoronene prepared in step S1, 0.55 g of ammonium fluoride, and 0.7 g of boric acid and place them in a 100 mL microwave reactor. Then add 42 mL of polyethyleneimine and 14 mL of N,N-dimethylformamide (DMF). After stirring evenly, place the microwave reactor into the reactor. Set the microwave power to 500 W, control the microwave reaction temperature at 255 °C, and the microwave reaction time to 2.6 h. The addition of ammonium fluoride and boric acid in this step can obtain F and B co-doped graphene quantum dots. Under the action of microwave heating, nitrocoronene and polyethyleneimine can be used to prepare graphene quantum dots. Microwave heating has the characteristics of instantaneity and rapidity, and can prepare smaller materials, which is beneficial to the synthesis of graphene quantum dots. There is a synergistic effect between F and B, and the two jointly change the electronic structure around the graphene quantum dots, enabling them to better combine with other nanoparticles.

[0067] S3. Weigh 0.58 g of 2-aminoterephthalic acid and place it in a 100 mL polytetrafluoroethylene reactor. Measure 16 mL of DMF and 18 mL of anhydrous methanol and add them to the above reactor. Then quickly add 0.9 mL of titanium tetraisopropoxide and 0.5 g of copper nitrate to the reactor and stir evenly. Place the polytetrafluoroethylene reactor into a stainless steel reactor jacket, and then put it into an electrothermal constant temperature blast drying oven. Heat-treat it at 190 °C for 15 h. After the reaction is completed, wait for the reactor to cool to room temperature, centrifuge to remove the supernatant, wash the yellow precipitate 4 times with anhydrous DMF and anhydrous methanol respectively, centrifuge to remove the DMF and methanol solutions, collect the yellow precipitate, and vacuum dry it at 80 °C for 12 h to obtain the metal-organic framework of nano polyhedron Ti-Cu.

[0068] S4. Weigh 0.44 g of the metal-organic framework of Ti-Cu prepared in step S3 and lay it flat in a ceramic boat. Place the ceramic boat in the middle part of the quartz tube of the tube furnace. Under an air atmosphere, set the tube furnace to heat up to 750 °C at a heating rate of 5 °C / min and keep it warm for 3 h. After natural cooling, Ti / Cu-O can be obtained. x This step converts the metal-organic framework of Ti-Cu into Ti / Cu-O. x It can combine the advantages of MOF and the advantages of oxides. Combining Ti / Cu-O x with the F and B co-doped graphene quantum dots prepared in step S2 can better play an antibacterial role and help improve the cleaning effect. In addition, the specific surface area of Ti / Cu-O x prepared using the metal-organic framework of Ti-Cu is relatively large, and it can well adsorb the dirt on the surface.

[0069] S5. Weigh 26 g of jasmine flowers, 31 g of green tea, 6 g of mint leaves and 10 g of ginger, mix them evenly, grind and crush them, then add 250 mL of deionized water, boil for 10 times, 30 minutes each time, combine the filtrates, and obtain the plant extract by distillation. In the mixed extract prepared in this step, natural herbs such as jasmine flowers, green tea, mint leaves and ginger complement each other and have a certain inhibitory effect on different bacteria. Using it in the washing liquid can better enhance the antibacterial effect.

[0070] S6. Heat 280 mL of deionized water to 58 °C, and successively add 22 ml of glycerol, 1.5 g of cetyltrimethylammonium bromide (CTAB), 2.2 g of the F, B-doped graphene quantum dots prepared in step S2, and 0.4 g of Ti / Cu-O prepared in step S4 x , when the temperature drops to 28 °C, then add 17 g of sodium carboxymethyl cellulose and 5 g of sodium dodecyl sulfate (SDS), then add 70 mL of the plant extract prepared in step S5 while stirring, and finally adjust the pH to 7.2 with a trisodium citrate aqueous solution to make the hair conditioner containing antibacterial graphene quantum dots. In this step, Ti / Cu-O x can be tightly combined with graphene quantum dots through π-π interaction, and the F, B-doped graphene quantum dots are negatively charged around and can attract metal ions through electrostatic interaction. Combine Ti / Cu-O x with graphene quantum dots, and the attraction between them can thermodynamically weaken the tendency of material aggregation, which is beneficial to improving the antibacterial activity of the material. In addition, graphene quantum dots and Ti / Cu-O x complement each other, cooperate with the plant extract, can play a good antibacterial and cleaning effect, and the high specific surface area is beneficial to adsorbing dirt.

[0071] Comparative Example 6: In step S6, except for not adding 1.5 g of cetyltrimethylammonium bromide (CTAB), the other steps are the same as those in Example 4.

[0072] Comparative Example 7: In step S6, except for using graphene to replace the F, B-doped graphene quantum dots prepared in the present invention, the other steps are the same as those in Example 4.

[0073] Comparative Example 8: In step S6, except for not adding Ti / Cu-O x , the other steps are the same as those in Example 4.

[0074] Comparative Example 9: Select a commercially available hair conditioner.

[0075] The combing experiment is the best method to evaluate the smoothness effect of hair conditioners. The smaller the combing work, the smaller the force between the hair and the comb, and the smoother the hair. In this invention, the combing instrument selected is the Techno Hashimoto SK-7A dynamic hair combing instrument. The hair conditioners prepared in Examples 3 and 4 of this invention were compared with the hair conditioners prepared in Comparative Examples 6-9 in terms of combability. Table 2 records the combing work after using the hair conditioners. The analysis shows that in the wet experiment, the combing work of the hair conditioners prepared in Examples 3 and 4 of this invention is significantly lower than that of the hair conditioners prepared in Comparative Examples 6-9. The reason for the analysis is the electrostatic adsorption between cetyltrimethylammonium bromide surfactant and graphene quantum dots. The plant extract is adsorbed on the hair surface to play a smoothing role. And the addition of Ti / Cu-O x enhances and stimulates the antibacterial activity of graphene quantum dots. Ti / Cu-O x can be tightly combined with graphene quantum dots through π-π interaction. And the F- and B-doped graphene quantum dots are negatively charged around, and can attract metal ions through electrostatic interaction. The two interact with each other to jointly promote the adsorption of nutrients in the hair conditioner onto the hair surface, so as to improve the silkiness of the hair. The combing experiment shows that the wet combability of the hair conditioner prepared in this invention is better than that of the commercially available hair conditioner. The hair cutin scales are regular and do not warp after being treated with the hair conditioner prepared in this invention, which is suitable for popularization and application.

[0076] Table 2. Record form of the combing experiment of hair conditioners

[0077]

[0078] The above-described embodiments only represent the specific implementation manners of the present invention. The description is relatively specific and detailed, but it should not be construed as a limitation on the protection scope of the present invention. It should be noted that for those of ordinary skill in the art, without departing from the concept of the present invention, any other changes, modifications, substitutions, combinations, and simplifications made under the premise of not deviating from the spirit and principle of the present invention shall be equivalent replacement methods and are all included in the protection scope of the present invention.

Claims

1. An antibacterial graphene quantum dot, characterized in that: The specific preparation method is as follows: S1. Add 5-7 g of coronene to 30-50 ml of concentrated nitric acid, keep warm at 55-60 °C for 4-6 h to synthesize nitrocoronene, remove excess nitric acid by centrifugation, and then wash with N,N-dimethylformamide DMF for 3-5 times; S2. Take 2-3 g of nitrobenzene prepared in step S1, 0.4-0.6 g of ammonium fluoride and 0.5-0.8 g of boric acid and place them in a 100 mL microwave reactor, then add 35-45 mL of polyethyleneimine and 12-15 mL of N,N-dimethylformamide DMF, stir evenly, and place the microwave reactor into the reactor; set the microwave power to 300-600 W, the microwave reaction temperature to 220-260 ° C, and the microwave reaction time to 2-3 h; F and B doped graphene quantum dots can be obtained.

2. A hair conditioner containing antibacterial graphene quantum dots, characterized in that: The specific preparation method is as follows: S1. Add 5-7 g of coronene to 30-50 ml of concentrated nitric acid, keep warm at 55-60 °C for 4-6 h to synthesize nitrocoronene, remove excess nitric acid by centrifugation, and then wash with N,N-dimethylformamide DMF 3-5 times; S2, take 2-3 g of nitrocoronene prepared in step S1, 0.4-0.6 g of ammonium fluoride and 0.5-0.8 g of boric acid and place them in a 100 mL microwave reactor, then add 35-45 mL of polyethyleneimine and 12-15 mL of N,N-dimethylformamide DMF, stir evenly, and place the microwave reactor in the reactor; set the microwave power to 300-600 W, the microwave reaction temperature to 220-260 ° C, and the microwave reaction time to 2-3 h; F, B doped graphene quantum dots can be obtained; S3, weigh 0.5-0.7 g of 2-aminoterephthalic acid in a 100 mL polytetrafluoroethylene reactor, measure 13-17 mL DMF and 13-21 mL anhydrous methanol and add them to the above reactor, then quickly add 0.8-1.1 mL of tetraisopropyl titanate and 0.5 g of copper nitrate to the reactor, and stir them evenly; put the polytetrafluoroethylene reactor into a stainless steel reactor sleeve, and then put it into an electric constant temperature blast drying oven, and heat treat it at 180-200 ° C for 12-16 h; after the reaction is completed, wait for the reactor to cool to room temperature, centrifuge to remove the supernatant, wash the yellow precipitate with anhydrous DMF and anhydrous methanol for 3-5 times respectively, centrifuge to remove DMF and methanol solution, collect the yellow precipitate, and vacuum dry it at 80 ° C for 12 h to obtain a metal organic framework of nano-polyhedron Ti-Cu; S4, weigh 0.4-0.5 g of the Ti-Cu metal organic framework prepared in step S3 and spread it flat in a ceramic ark, put the ceramic ark into the middle part of the quartz tube of a tube furnace, set the tube furnace to heat up to 750 ° C at a heating rate of 5 ° C / min in an air atmosphere, and keep it warm for 2-3 h, and then cool it naturally to obtain Ti / Cu-O x ; S5, heat 220-260 mL of deionized water to 58 °C, and add 20-25 ml of glycerol, 1.2-1.8 g of hexadecyltrimethylammonium bromide, 1.1-2.6 g of F, B doped graphene quantum dots prepared in step S2, and 0.3-0.5 g of Ti / Cu-O prepared in step S4 in sequence at this temperature; x When the temperature drops to 28 °C, add 15-20 g of sodium hydroxymethyl cellulose and 5 g of sodium dodecyl sulfate, then add 50-80 mL of plant extract while stirring, and finally adjust the pH to 6.9-7.3 with trisodium citrate aqueous solution to prepare a conditioner containing antibacterial graphene quantum dots.

3. A hair conditioner containing antibacterial graphene quantum dots according to claim 2, characterized in that: In the step S1, 5 g of coronene is added to 30 ml of concentrated nitric acid, and the mixture is kept warm at 55° C. for 4 h to synthesize nitrocoronene. Excess nitric acid is removed by centrifugation, and then the mixture is washed with N,N-dimethylformamide (DMF) for 5 times.

4. A hair conditioner containing antibacterial graphene quantum dots according to claim 3, characterized in that: In the step S2, 3 g of nitrobenzene prepared in step S1, 0.4 g of ammonium fluoride and 0.8 g of boric acid are placed in a 100 mL microwave reactor, and then 45 mL of polyethyleneimine and 12 mL of N,N-dimethylformamide DMF are added. After stirring evenly, the microwave reactor is placed in the reactor; the microwave power is set to 300 W, the microwave reaction temperature is controlled at 220 ° C, and the microwave reaction time is 3 h.

5. A hair conditioner containing antibacterial graphene quantum dots according to claim 2 or 3, characterized in that: In the step S2, 2 g of the nitrobenzene prepared in the step S1, 0.4 g of ammonium fluoride and 0.5 g of boric acid are placed in a 100 mL microwave reactor, and then 35 mL of polyethyleneimine and 12 mL of N,N-dimethylformamide DMF are added. After stirring evenly, the microwave reactor is placed in the reactor; the microwave power is set to 600 W, the microwave reaction temperature is controlled at 260 ° C, and the microwave reaction time is 3 h.

6. A hair conditioner containing antibacterial graphene quantum dots according to claim 5, characterized in that: In the step S3, 0.7 g of 2-aminoterephthalic acid is weighed into a 100 mL polytetrafluoroethylene reactor, 17 mL of DMF and 13 mL of anhydrous methanol are measured and added to the reactor, and then 1.1 mL of tetraisopropyl titanate and 0.5 g of copper nitrate are quickly added to the reactor and stirred evenly; the polytetrafluoroethylene reactor is placed in a stainless steel reactor jacket, and then placed in an electric constant temperature blast drying oven, and heat treated at 180°C for 16 h; after the reaction is completed, the reactor is cooled to room temperature, centrifuged to remove the supernatant, and the yellow precipitate is washed 5 times with anhydrous DMF and anhydrous methanol respectively, centrifuged to remove the DMF and methanol solutions, and the yellow precipitate is collected and vacuum dried at 80°C for 12 h to obtain a metal organic framework of nano-polyhedral Ti-Cu.

7. A hair conditioner containing antibacterial graphene quantum dots according to claim 2, characterized in that: In the step S4, 0.5 g of the Ti-Cu metal organic framework prepared in step S3 is weighed and laid flat in a ceramic ark, and the ceramic ark is placed in the middle part of the quartz tube of a tube furnace. In an air atmosphere, the tube furnace is set to heat up to 750 ° C at a heating rate of 5 ° C / min and kept at this temperature for 3 h. After natural cooling, the Ti / Cu-O x .

8. A hair conditioner containing antibacterial graphene quantum dots according to claim 2, characterized in that: In the step S4, 0.4 g of the Ti-Cu metal organic framework prepared in step S3 is weighed and laid flat in a ceramic ark, and the ceramic ark is placed in the middle part of the quartz tube of a tube furnace. In an air atmosphere, the tube furnace is set to heat up to 750 ° C at a heating rate of 5 ° C / min and kept at this temperature for 2 h. After natural cooling, the Ti / Cu-O x .

9. A hair conditioner containing antibacterial graphene quantum dots according to claim 8, characterized in that: In step S5, 220 mL of deionized water is heated to 58° C. At this temperature, 25 mL of glycerol, 1.2 g of hexadecyltrimethylammonium bromide, 2.6 g of F- and B-doped graphene quantum dots prepared in step S2, and 0.3 g of Ti / Cu-O prepared in step S4 are added in sequence. x When the temperature drops to 28 °C, add 20 g of sodium hydroxymethyl cellulose and 5 g of sodium dodecyl sulfate, then add 50-80 mL of plant extract while stirring, and finally adjust the pH to 7.3 with trisodium citrate aqueous solution to prepare a conditioner containing antibacterial graphene quantum dots.

10. A hair conditioner containing antibacterial graphene quantum dots according to claim 2, characterized in that: The method for preparing the plant extract described in step S5 is specifically as follows: weigh 26 g of jasmine, 31 g of green tea, 6 g of mint leaves and 10 g of ginger, mix them evenly, grind and mash them, add 250 mL of deionized water, boil them 10 times, each time for 30 min, combine the filtrate, and obtain the plant extract by distillation.

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