CN113278416B - Water-soluble pillararene modified amphiphilic graphene quantum dot, and preparation method and application thereof - Google Patents
Water-soluble pillararene modified amphiphilic graphene quantum dot, and preparation method and application thereof Download PDFInfo
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- ATALLSGKFZVRKF-UHFFFAOYSA-N 1,4-bis(2-bromoethoxy)benzene Chemical compound BrCCOC1=CC=C(OCCBr)C=C1 ATALLSGKFZVRKF-UHFFFAOYSA-N 0.000 claims description 12
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Abstract
The application discloses a water-soluble pillar aromatic modified amphiphilic graphene quantum dot, a preparation method and application. The water-soluble column arene modified amphiphilic graphene quantum dot comprises a water-soluble column arene modified amphiphilic graphene quantum dot obtained by modifying the amphiphilic graphene quantum dot with the water-soluble column arene, wherein the amphiphilic graphene quantum dot and the water-soluble column arene are combined through a hydrophobic effect and an electrostatic effect to form the water-soluble column arene modified amphiphilic graphene quantum dot. The preparation method is simple and easy to operate and good in repeatability; the prepared modified amphiphilic graphene quantum dot emits stronger green fluorescence, the fluorescence intensity is enhanced after the water-soluble column aromatic hydrocarbon is modified, the affinity is higher, the quantum dot can penetrate through a cell membrane more easily, and the modified amphiphilic graphene quantum dot has low toxicity and biocompatibility and can be used for cell imaging.
Description
Technical Field
The application relates to a water-soluble pillared aromatic hydrocarbon modified amphiphilic graphene quantum dot, a preparation method and application.
Background
Due to quantum confinement effect and boundary effect, graphene quantum dots are valued by people in fluorescent materials. Graphene Quantum Dots (GQDs) can be regarded as small graphite fragments, and are generally single-layer, double-layer or multi-layer (3-10) zero-dimensional graphite nano-materials with the transverse dimension of less than 100nm, and have unique fluorescence properties. At present, most of the synthesized graphene quantum dots are hydrophilic or lipophilic, and can only be used in a single solvent, so that the use condition of cell imaging of the graphene quantum dots is greatly limited. Traditional hydrophilic carbon dots or graphene quantum dots have poor affinity with cell membranes during imaging due to the existence of a hydrophobic interface, so that clear images cannot be obtained. Therefore, how to improve the affinity with the cell membrane during imaging is important to obtain a clear image.
Disclosure of Invention
In view of the above, the present invention aims to provide a preparation method and an application of a water-soluble pillar arene-modified amphiphilic graphene quantum dot with high affinity and wide application.
In order to achieve the purpose, the technical scheme of the invention is realized according to the following scheme:
the embodiment of the invention provides a water-soluble pillared aromatic hydrocarbon modified amphiphilic graphene quantum dot, which is modified by water-soluble pillared aromatic hydrocarbon to obtain the water-soluble pillared aromatic hydrocarbon modified amphiphilic graphene quantum dot.
The embodiment of the invention also provides a preparation method of the water-soluble pillared aromatic hydrocarbon modified amphiphilic graphene quantum dot, wherein the amphiphilic graphene quantum dot is taken and respectively mixed with the water-soluble pillared aromatic hydrocarbon in an aqueous solution to obtain the water-soluble pillared aromatic hydrocarbon modified amphiphilic graphene quantum dot. The amphiphilic graphene quantum dot modified by the water-soluble pillararene is formed by combining the amphiphilic graphene quantum dot and the water-soluble pillararene through hydrophobic interaction and electrostatic interaction.
A preparation method of water-soluble pillared aromatic hydrocarbon modified amphiphilic graphene quantum dots comprises the following steps: preparing amphiphilic graphene quantum dots; (2) preparing water-soluble pillar aromatic hydrocarbon; (3) Mixing the amphiphilic graphene quantum dots and water-soluble pillared aromatic hydrocarbons in an aqueous solution, combining alkyl chains on the amphiphilic graphene quantum dots with cavities of the pillared aromatic hydrocarbons through a hydrophobic effect, and combining ammonium salts with cations on the pillared aromatic hydrocarbons with hydroxyl groups on the amphiphilic graphene quantum dots through an electrostatic effect to obtain the amphiphilic graphene quantum dots modified by the water-soluble pillared aromatic hydrocarbons.
Further, the mixing in the step (3) is as follows: the mass ratio of the amphiphilic graphene quantum dots to the water-soluble column aromatic hydrocarbon is as follows: 1:1-4. Only in the mass ratio range, the water-soluble column aromatic hydrocarbon and the amphiphilic graphene quantum dot can be well combined, and the fluorescence performance of the amphiphilic graphene quantum dot is further improved.
Further, the preparation process of the amphiphilic graphene quantum dot obtained in the step (1) is as follows: selecting a compound capable of generating a hydrophilic group, a compound capable of generating a hydrophobic group and a carbon source compound, dissolving in a solvent to obtain a mixed liquid, and synthesizing the amphiphilic graphene quantum dot by a hydrothermal method.
Further, the carbon source compound is 1,3, 6-trinitropyrene; the compound capable of generating hydrophobic groups is lauric acid; the compound capable of generating hydrophilic groups is sodium hydroxide.
Further, the step (1) is as follows: carrying out hydro-thermal reaction on a mixed aqueous solution of 1,3, 6-trinitropyrene, lauric acid and sodium hydroxide for a certain time, dialyzing, purifying and freeze-drying the obtained solution to obtain an amphiphilic graphene quantum dot solid; wherein the concentration of 1,3, 6-trinitropyrene is 2.0mg/ml, the concentration of lauric acid is 10.0mg/ml, the concentration of sodium hydroxide is 5.0mg/ml, the hydrothermal reaction temperature is 200 ℃, and the reaction time is 10 hours; and dialyzing the reaction product by a dialysis bag with the molecular weight cutoff of 1000Da, and collecting to obtain the amphiphilic graphene quantum dots.
Further, the preparation process of the water-soluble pillar arene in the step (2) comprises the following steps: (2.1) dissolving 1, 4-bis (2-bromoethoxy) benzene in 1, 2-dichloroethane, and adding paraformaldehyde under a nitrogen environment to form a solution I; (2.2) adding boron trifluoride diethyl ether into the solution I in the step (2.1), and stirring to obtain a green solution; (2.3) removing the solvent in the green solution obtained in the step (2.2), and purifying by silica gel column chromatography by using petroleum ether/dichloromethane as an eluent to obtain white powder, namely a compound I;
(2.4) adding the compound I and trimethylamine into ethanol, and refluxing; then evaporating to remove the solvent, and adding deionized water; filtering to obtain clear solution; finally, evaporating water to obtain colorless solid, namely the target product water-soluble column aromatic hydrocarbon.
Further, the specific preparation method of the compound I comprises the following steps: 3.37g of 11.5mmol of 1, 4-bis (2-bromoethoxy) benzene was dissolved in 200mL of 1, 2-dichloroethane, and 0.349g of 11.5mmol of paraformaldehyde was added under a nitrogen-filled atmosphere; then, 1.63g of 11.5mmol of boron trifluoride diethyl ether was added to the solution, and the mixture was stirred at room temperature for 3 hours to obtain a green solution; after the solvent of the solution was removed, 1.6g of white powder, i.e., compound one, was obtained by silica gel column chromatography purification using petroleum ether/dichloromethane as the eluent.
Further, the preparation method of the 1, 4-bis (2-bromoethoxy) benzene comprises the following steps: 3.303g,30mmol of hydroquinone and 11.056g,80mmol of anhydrous potassium carbonate are mixed and stirred for 2 hours at the temperature of 60 ℃ under the nitrogen atmosphere; then, 40mL of excess 1, 2-dibromoethane was added; stirring the reaction mixture for 24 hours at the temperature of 60 ℃ under the nitrogen atmosphere, and filtering; evaporating the filtrate by using a rotary evaporator to remove the 1, 2-dibromoethane and the solvent; the residue was dissolved in 100mL of chloroform, washed with 50mL of sodium hydroxide solution and then 50mL of water; drying the extract over anhydrous magnesium sulfate; removal of CHCl 3 Vacuum drying at 40 ℃ gave 1, 4-bis (2-bromoethoxy) benzene as a light brown powder.
Further, the application of the water-soluble column aromatic modified amphiphilic graphene quantum dot prepared by the method is characterized by being used for imaging and biosensing cells.
According to the method, the amphiphilic graphene quantum dots and the water-soluble pillararene are combined through hydrophobic effect and electrostatic effect to form the amphiphilic graphene quantum dots modified by the water-soluble pillararene. The use conditions of cell imaging of the graphene quantum dots can be widened by means of the amphiphilic graphene quantum dots, and the amphiphilic graphene quantum dots are modified by using organic water-soluble column aromatic hydrocarbon, so that the affinity with cell membranes is improved during imaging, and clear images are obtained; in addition, the water-soluble column aromatic modified amphiphilic graphene quantum dot has high binding force, improves the fluorescence property of the amphiphilic graphene quantum dot, and can be used for cell imaging. The method for preparing the water-soluble pillared aromatic hydrocarbon can obtain the water-soluble pillared aromatic hydrocarbon with high yield (95%), can be directly used for later modification, and avoids the introduction of impurities. The method is simple and good in repeatability.
Drawings
FIGS. 1a and 1b are synthetic diagrams of water-soluble pillar aromatics in the examples of this application.
FIG. 2 is a nuclear magnetic resonance image of water-soluble pillararene according to the example of the present application.
Fig. 3a is a transmission electron microscope image of an amphiphilic graphene quantum dot in an embodiment of the present application.
Fig. 3b is a transmission electron microscope image of the amphiphilic graphene quantum dots with high resolution in the embodiment of the present application.
Fig. 4 is a fluorescence emission spectrum of amphiphilic graphene quantum dots according to an embodiment of the present application.
Fig. 5 is a Zeta potential diagram of water-soluble pillararene, amphiphilic graphene quantum dots, and water-soluble pillararene-modified amphiphilic graphene quantum dots according to the embodiment of the present application.
Fig. 6 is a diagram of an ultraviolet-visible absorption spectrum of water-soluble pillar arene, amphiphilic graphene quantum dots, and water-soluble pillar arene-modified amphiphilic graphene quantum dots according to an embodiment of the present application.
Fig. 7 shows the ratio of amphiphilic graphene quantum dots to water-soluble pillar arene in the ratio of 1:1-4, and mixing to obtain the water-soluble pillaraarene modified amphiphilic graphene quantum dot.
Fig. 8 is a cell imaging diagram of the water-soluble pillararene-modified amphiphilic graphene quantum dot and the amphiphilic graphene quantum dot under a laser confocal microscope according to the embodiment of the present application.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments.
The embodiment of the invention provides a water-soluble pillared aromatic hydrocarbon modified amphiphilic graphene quantum dot, which is modified by water-soluble pillared aromatic hydrocarbon to obtain the water-soluble pillared aromatic hydrocarbon modified amphiphilic graphene quantum dot. The amphiphilic graphene quantum dot modified by the water-soluble column aromatic hydrocarbon is formed by combining the amphiphilic graphene quantum dot and the water-soluble column aromatic hydrocarbon through hydrophobic interaction and electrostatic interaction.
The amphiphilic graphene quantum dot modified by the water-soluble column aromatic hydrocarbon has strong affinity with a cell membrane, and a clear image can be obtained during cell imaging.
The embodiment of the invention also provides a preparation method of the water-soluble pillared aromatic hydrocarbon modified amphiphilic graphene quantum dot, wherein the amphiphilic graphene quantum dot is taken and respectively mixed with the water-soluble pillared aromatic hydrocarbon in an aqueous solution to obtain the water-soluble pillared aromatic hydrocarbon modified amphiphilic graphene quantum dot. The amphiphilic graphene quantum dot modified by the water-soluble column aromatic hydrocarbon is formed by combining the amphiphilic graphene quantum dot and the water-soluble column aromatic hydrocarbon through hydrophobic interaction and electrostatic interaction. The binding force of the two is improved, and the stability of the amphiphilic graphene quantum dots modified by the water-soluble column aromatic hydrocarbon is improved.
A preparation method of water-soluble pillared aromatic hydrocarbon modified amphiphilic graphene quantum dots comprises the following steps: preparing amphiphilic graphene quantum dots; (2) preparing water-soluble pillar aromatic hydrocarbon; (3) Mixing the amphiphilic graphene quantum dot and water-soluble column aromatic hydrocarbon in an aqueous solution, combining an alkyl chain on the amphiphilic graphene quantum dot with a cavity of the column aromatic hydrocarbon through a hydrophobic effect, and combining an ammonium salt with cations on the column aromatic hydrocarbon with a hydroxyl on the amphiphilic graphene quantum dot through an electrostatic effect to obtain the water-soluble column aromatic hydrocarbon modified amphiphilic graphene quantum dot.
The mixing in the step (3) is as follows: the mass ratio of the amphiphilic graphene quantum dots to the water-soluble column aromatic hydrocarbon is as follows: 1:1-4. Only in the mass ratio range, the water-soluble column aromatic hydrocarbon and the amphiphilic graphene quantum dot can be well combined, and the fluorescence performance of the amphiphilic graphene quantum dot is further improved.
The preparation process of the amphiphilic graphene quantum dot obtained in the step (1) is as follows: selecting a compound capable of generating a hydrophilic group, a compound capable of generating a hydrophobic group and a carbon source compound, dissolving in a solvent to obtain a mixed liquid, and synthesizing the amphiphilic graphene quantum dot by a hydrothermal method. The carbon source compound is 1,3, 6-trinitropyrene; the compound capable of generating hydrophobic groups is lauric acid; the compound capable of generating hydrophilic groups is sodium hydroxide.
The preparation process of the water-soluble pillar aromatic hydrocarbon in the step (2) comprises the following steps: (2.1) dissolving 1, 4-bis (2-bromoethoxy) benzene in 1, 2-dichloroethane, and adding paraformaldehyde under a nitrogen environment to form a solution I; (2.2) adding boron trifluoride diethyl ether into the solution I in the step (2.1), and stirring to obtain a green solution; and (2.3) removing the solvent in the green solution obtained in the step (2.2), and purifying by silica gel column chromatography by using petroleum ether/dichloromethane as an eluent to obtain white powder, namely the compound I.
(2.4) adding the compound I and trimethylamine into ethanol, and refluxing; then evaporating to remove the solvent, and adding deionized water; filtering to obtain a clear solution; finally, evaporating water to obtain colorless solid, namely the target product water-soluble column aromatic hydrocarbon.
Example 1
The embodiment of the invention provides a preparation method of water-soluble pillared aromatic modified amphiphilic graphene quantum dots, which comprises the following specific steps:
step 1: 3.3.3g,30mmol of hydroquinone and 11.056g,80mmol of anhydrous potassium carbonate were mixed in a 250mL three-round bottom flask and stirred at 60 ℃ under nitrogen for 2h. Then, 40mL of excess 1, 2-dibromoethane was added. The reaction mixture was stirred at 60 ℃ under a nitrogen atmosphere for 24h and filtered. The filtrate is steamed by rotationThe evaporator was evaporated to remove 1, 2-dibromoethane and solvent. The residue was dissolved in 100mL of chloroform, washed three times with 50mL of sodium hydroxide solution and twice with 50mL of water. The extract was dried over anhydrous magnesium sulfate. Removal of CHCl 3 Vacuum drying at 40 deg.C gave 35% pure 1, 4-bis (2-bromoethoxy) benzene as a light brown powder, which is synthesized as shown in FIG. 1 a.
Step 2: 3.37g of 11.5mmol of 1, 4-bis (2-bromoethoxy) benzene was dissolved in 200mL of 1, 2-dichloroethane, and 0.349g of 11.5mmol of paraformaldehyde was added under a nitrogen-filled atmosphere. Then, 1.63g of 11.5mmol of boron trifluoride diethyl ether was added to the solution, and the mixture was stirred at room temperature for 3 hours to obtain a green solution. After the solvent of the solution was removed, the mixture was purified by silica gel column chromatography using petroleum ether/dichloromethane as eluent to obtain 1.6g of white powder (41%) as compound one.
And step 3: 1.0 g of 0.595mmol of the first compound and 6.43mL of 23.8mmol of trimethylamine (33% ethanol solution) are added to 50mL of ethanol and refluxed. The solvent was then evaporated and 20mL of deionized water was added. After filtration a clear solution was obtained. Finally, water is evaporated to obtain 1.28g of colorless solid (95%), namely the target product water-soluble column aromatic hydrocarbon.
And 4, step 4: carrying out hydrothermal reaction on a mixed aqueous solution of 1,3, 6-trinitropyrene, lauric acid and sodium hydroxide for a certain time, dialyzing and purifying the obtained solution, and further carrying out freeze drying to obtain the amphiphilic graphene quantum dot solid. Wherein the concentration of 1,3, 6-trinitropyrene is 2.0mg/ml, the concentration of lauric acid is 10.0mg/ml, the concentration of sodium hydroxide is 5.0mg/ml, the hydrothermal reaction temperature is 200 ℃, and the hydrothermal reaction time is 10 hours. And (3) fully dialyzing the reaction product by a dialysis bag with the molecular weight cutoff of 1000Da, and collecting to obtain the amphiphilic graphene quantum dots.
And 5: taking 5mg of amphiphilic graphene quantum dots, and mixing the amphiphilic graphene quantum dots with water-soluble pillared aromatic hydrocarbons in 5mL of aqueous solution according to the mass ratio of 1, 1.
The hydrophilic column arene, the amphiphilic graphene quantum dot and the amphiphilic graphene quantum dot modified by the hydrophilic column arene in the embodiment 1 are subjected to test characterization such as nuclear magnetic resonance, transmission electron microscopy, X-ray photoelectron spectroscopy, electrostatic interaction, fluorescence spectroscopy and laser confocal microscopy, and the obtained test results are shown in fig. 1 to 8.
FIG. 1a and FIG. 1b are the synthesis diagrams of water-soluble pillar aromatic hydrocarbons. The reaction of FIG. 1a produced 1, 4-bis (2-bromoethoxy) benzene in 85% yield, the first step in FIG. 1b produced compound one in 41% yield, and the last step produced water-soluble pillararene in 95% yield. The preparation method can be used for simply obtaining the water-soluble column aromatic hydrocarbon with high yield.
FIG. 2 is a water-soluble pillararene NMR chart. At 400MHz, room temperature, with D 2 O as a solvent, 6.986 (s, 10H), 4.489 (s, 20H), 3.960 (s, 10H), 3.844 (s, 20H), 3.248 (s, 90H) were measured. It is apparent that the process of the present application results in water-soluble pillared aromatics of high purity.
Fig. 3a is a transmission electron micrograph of amphiphilic graphene quantum dots, and fig. 3b is a high-resolution transmission electron micrograph of amphiphilic graphene quantum dots. The scale in FIG. 3a is 100nm and the scale in FIG. 3b is 10nm. It can be seen from fig. 3a that the amphiphilic graphene quantum dots modified by the hydrophilic column aromatic hydrocarbon are agglomerated to a certain extent, the particle size range after agglomeration is 10-80nm, and it can be seen from fig. 3b that the size of the amphiphilic graphene quantum dots modified by the hydrophilic column aromatic hydrocarbon is about 2-5 nm, the average particle size is 3.5nm, the lattice spacing is 0.24nm, and the size is relatively uniform.
Fig. 4 is a fluorescence emission spectrum of the amphiphilic graphene quantum dot. The range of the excitation wavelength is 410nm to 490nm, and the maximum emission wavelength obtained at the optimum excitation wavelength of 490nm is 540nm. It can be seen that the amphiphilic graphene quantum dots have fluorescence characteristics independent of excitation wavelength, and the particle size is proved to be uniform.
FIG. 5 is a Zeta point diagram of water soluble pillar arene (WP 5), amphiphilic Graphene Quantum Dots (GQDs), and water soluble pillar arene modified amphiphilic graphene quantum dots (WP 5/GQDs). As can be seen from fig. 5, the amphiphilic graphene quantum dot is negatively charged, the water-soluble pillar aromatic hydrocarbon is positively charged, and the amphiphilic graphene quantum dot modified by the water-soluble pillar aromatic hydrocarbon is finally negatively charged, so that the water-soluble pillar aromatic hydrocarbon and the amphiphilic graphene quantum dot can have electrostatic and hydrophobic effects, and the binding force of the amphiphilic graphene quantum dot is further improved.
FIG. 6 is a UV-Vis absorption spectrum of water soluble pillared aromatics (WP 5), amphiphilic Graphene Quantum Dots (GQDs) and water soluble pillared aromatic modified amphiphilic graphene quantum dots (WP 5/GQDs). The soluble pillared aromatic modified amphiphilic graphene quantum dots (WP 5/GQDs) have wide absorption bands when the size is less than 550 nm. As the column aromatic hydrocarbon increases the rigid structure, the absorption peak of the nano particles is red-shifted after the composition, and the light absorption performance of the amphiphilic graphene quantum dots is enhanced.
Fig. 7 is a fluorescence emission spectrum of a water-soluble pillared arene modified amphiphilic graphene quantum dot prepared by mixing an amphiphilic graphene quantum dot and water-soluble pillared arene in a mass ratio of 1 to 4, wherein the fluorescence emission spectra of the amphiphilic graphene quantum dot and the water-soluble pillararene respectively are represented by 1. When the mass ratio of the amphiphilic graphene quantum dots to the water-soluble pillared aromatic hydrocarbons is 1.
FIG. 8 is a cell imaging image of amphiphilic graphene quantum dots (WP 5/GQDs) and amphiphilic Graphene Quantum Dots (GQDs) modified by water-soluble pillar arene under a laser confocal microscope. It can be seen that under 488nm laser, the unmodified amphiphilic graphene quantum dots have brighter fluorescence at the cell membrane, and a small part of the fluorescence enters the cytoplasm. The amphiphilic graphene quantum dots modified by the water-soluble column aromatic hydrocarbon have bright fluorescence in the whole cell, and the result shows that the amphiphilic graphene quantum dots modified by the water-soluble column aromatic hydrocarbon obtained by the method have high affinity with a cell membrane during imaging, so that a clear image is obtained.
The embodiment of the application also comprises a second technical scheme, and the application of the water-soluble column arene modified amphiphilic graphene quantum dot prepared by the method of the embodiment of the application can be used for imaging and biosensing cells.
Claims (7)
1. A preparation method of water-soluble pillared aromatic hydrocarbon modified amphiphilic graphene quantum dots is characterized by comprising the following steps: (1) Preparing an amphiphilic graphene quantum dot, wherein the preparation of the amphiphilic graphene quantum dot comprises the steps of carrying out hydrothermal reaction on a mixed aqueous solution of 1,3, 6-trinitropyrene, lauric acid and sodium hydroxide for a certain time, dialyzing, purifying and freeze-drying the obtained solution to obtain an amphiphilic graphene quantum dot solid; (2) Preparing water-soluble pillar aromatic hydrocarbon, wherein the preparation process of the water-soluble pillar aromatic hydrocarbon comprises the following steps: (2.1) dissolving 1, 4-bis (2-bromoethoxy) benzene in 1, 2-dichloroethane, and adding paraformaldehyde under a nitrogen environment to form a solution I; (2.2) adding boron trifluoride diethyl ether into the solution I in the step (2.1), and stirring to obtain a green solution; (2.3) removing the solvent in the green solution obtained in the step (2.2), and purifying by silica gel column chromatography by using petroleum ether/dichloromethane as an eluent to obtain white powder, namely a compound I; (2.4) adding the compound I and trimethylamine into ethanol, and refluxing; then evaporating to remove the solvent, and adding deionized water; filtering to obtain a clear solution; finally, evaporating water to obtain a colorless solid, namely the target product water-soluble column aromatic hydrocarbon; (3) Mixing the amphiphilic graphene quantum dot and water-soluble column aromatic hydrocarbon in an aqueous solution, combining an alkyl chain on the amphiphilic graphene quantum dot with a cavity of the column aromatic hydrocarbon through a hydrophobic effect, and combining an ammonium salt with cations on the column aromatic hydrocarbon with a hydroxyl on the amphiphilic graphene quantum dot through an electrostatic effect to obtain the water-soluble column aromatic hydrocarbon modified amphiphilic graphene quantum dot.
2. The preparation method of the water-soluble pillar arene-modified amphiphilic graphene quantum dot according to claim 1, wherein the mixing in the step (3) is: the mass ratio of the amphiphilic graphene quantum dots to the water-soluble pillared aromatic hydrocarbons is as follows: 1:1-4.
3. The preparation method of the water-soluble pillared aromatic hydrocarbon modified amphiphilic graphene quantum dot according to claim 1, wherein in the step (1), the concentration of 1,3, 6-trinitropyrene is 2.0mg/ml, the concentration of lauric acid is 10.0mg/ml, the concentration of sodium hydroxide is 5.0mg/ml, the hydrothermal reaction temperature is 200 ℃, and the reaction time is 10 hours.
4. The preparation method of the water-soluble pillar arene-modified amphiphilic graphene quantum dot according to claim 1, wherein the specific preparation method of the first compound is as follows: 3.37g of 11.5mmol of 1, 4-bis (2-bromoethoxy) benzene was dissolved in 200mL of 1, 2-dichloroethane, and 0.349g of 11.5mmol of paraformaldehyde was added under a nitrogen-filled atmosphere; then, 1.63g of 11.5mmol of boron trifluoride diethyl ether was added to the solution, and the mixture was stirred at room temperature for 3 hours to obtain a green solution; removing the solvent of the solution, and purifying by silica gel column chromatography to obtain white powder, namely the compound I, by using petroleum ether/dichloromethane as an eluent.
5. The preparation method of the water-soluble pillar arene-modified amphiphilic graphene quantum dot according to claim 1, wherein the preparation method of the 1, 4-bis (2-bromoethoxy) benzene is as follows: 3.303g,30mmol of hydroquinone and 11.056g,80mmol of anhydrous potassium carbonate are mixed and stirred for 2 hours at the temperature of 60 ℃ under the nitrogen atmosphere; then, 40mL of excess 1, 2-dibromoethane was added; stirring the reaction mixture for 24 hours at 60 ℃ under a nitrogen atmosphere, and filtering; evaporating the filtrate by using a rotary evaporator to remove the 1, 2-dibromoethane and the solvent; the residue was dissolved in 100mL of chloroform, washed with 50mL of sodium hydroxide solution and 50mL of water; drying the extract over anhydrous magnesium sulfate; CHCl3 was removed and dried under vacuum at 40 ℃ to give 1, 4-bis (2-bromoethoxy) benzene as a light brown powder.
6. The water-soluble pillararene modified amphiphilic graphene quantum dot is characterized by being prepared by the preparation method of the water-soluble pillararene modified amphiphilic graphene quantum dot in any one of claims 1 to 5, wherein the water-soluble pillararene modified amphiphilic graphene quantum dot is obtained by modifying the amphiphilic graphene quantum dot with water-soluble pillararene, and the amphiphilic graphene quantum dot and the water-soluble pillararene are combined through hydrophobic interaction and electrostatic interaction to form the water-soluble pillararene modified amphiphilic graphene quantum dot.
7. The application of the water-soluble pillararene modified amphiphilic graphene quantum dot in the claim 6 is used for imaging and biosensing cells.
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