Fluorescent nanomaterial and preparation method and applications thereof

Abstract

The present disclosure provides a fluorescent nanomaterial and a preparation method and applications thereof, and the preparation method comprises: subjecting amphiphilic molecules in a solvent system to an illumination treatment and/or a heat treatment to obtain fluorescent nanomaterials. The preparation of fluorescent nanomaterials provided by the present disclosure is simple in process, simple and easily available in raw materials and requires neither additional addition of a strong acid, a strong alkali, a passivating agent and the like, nor high temperature and high pressure in the preparation process. The whole process is environmentally friendly and pollution-free and the products can be used in various fields.

Claims

1. A preparation method of fluorescent nanomaterials, wherein the preparation method comprises: subjecting amphiphilic molecules in a solvent system to an illumination treatment and/or a heat treatment to obtain fluorescent nanomaterials; wherein the amphiphilic molecules are subjected to an illumination treatment and then a heat treatment to obtain a mixture of hydrophilic fluorescent vesicles and hydrophobic fluorescent micelles.

2. The preparation method according to claim 1, wherein the fluorescent nanomaterials comprise any one selected from the group consisting of fluorescent vesicles, fluorescent micelles, fluorescent carbon nanoparticles, and a combination of at least two selected therefrom.

3. The preparation method according to claim 1, wherein the amphiphilic molecules comprise any one selected from the group consisting of a phosphatide, an aliphatic acid, an aliphatic alcohol, an aliphatic amine, an aliphatic aldehyde, a surfactant, a hyperbranched polymer, and a combination of at least two selected therefrom.

4. The preparation method according to claim 1, wherein the phosphatide comprises phosphoglyceride and/or sphingomyelin; the aliphatic acid comprises any one selected from the group consisting of a short-chain aliphatic acid, a medium-chain aliphatic acid, a long-chain aliphatic acid, and a combination of at least two selected therefrom; the aliphatic amine comprises any one selected from the group consisting of hexamethylenediamine, nonylamine, octylamine, octadecylamine, and a combination of at least two selected therefrom; the aliphatic aldehyde comprises any one selected from the group consisting of valeraldehyde, nonaldehyde, octanaldehyde, and a combination of at least two selected therefrom; the surfactant comprises any one selected from the group consisting of a cationic surfactant, an anionic surfactant, a nonionic surfactant, and a combination of at least two selected therefrom; the hyperbranched polymer comprises any one selected from the group consisting of hyperbranched aromatic polyether ketone, methyl methacrylate, hyperbranched poly(amine-ester), hyperbranched polyphenyl, poly(ethylene glycol) methyl ether, and a combination of at least two selected therefrom.

5. The preparation method according to claim 4, wherein the cationic surfactant comprises any one selected from the group consisting of an amine-salt-type surfactant, a quaternary-ammonium-salt-type surfactant, a heterocyclic-type surfactant, an onium-salt-type surfactant, and a combination of at least two selected therefrom; the anionic surfactant comprises any one selected from the group consisting of a polyacrylamide, a sulfonate, a sulfate, a phosphate, and a combination of at least two selected therefrom; the nonionic surfactant comprises a polyoxyethylene-type surfactant and/or a polyol-type surfactant.

6. The preparation method according to claim 1, wherein the amphiphilic molecules are subjected to an illumination treatment to obtain fluorescent vesicles; the fluorescent vesicles have a diameter of 9 nm-10 μm.

7. The preparation method according to claim 6, wherein the fluorescent vesicles are subjected to a treatment to obtain fluorescent carbon nanoparticles; the fluorescent carbon nanoparticles have a diameter of 1 nm-100 nm; the means of the treatment comprises: performing any one or at least two means selected from the group consisting of standing, centrifuging, dialyzing, adding a salt, extracting and chromatographic separation on the fluorescent vesicle solution, and destroying the vesicles to obtain fluorescent carbon nanoparticles.

8. The preparation method according to claim 1, wherein the amphiphilic molecules are subjected to a heat treatment to obtain fluorescent micelles; the fluorescent micelles are subjected to a treatment to obtain fluorescent carbon nanoparticles; the means of the treatment comprises: performing any one or at least two means selected from the group consisting of centrifuging, dialyzing, adding a salt, extracting and chromatographic separation on the fluorescent micelles, and destroying the micelles to obtain fluorescent carbon nanoparticles.

9. The preparation method according to claim 1, wherein the concentration of the amphiphilic molecules in the solvent system is 0.01 mM-1000 mM.

10. The preparation method according to claim 1, wherein the wavelength for the illumination treatment is 100 nm-2500 nm, and the illumination treatment is for a time of 0.1 h-100 h.

11. The preparation method according to claim 1, wherein the means of the heat treatment comprises any one selected from the group consisting of rotary evaporation, vacuum distillation and atmospheric distillation, the heat treatment is for a time of 0.1 h-48 h; and the temperature for the heat treatment is 30° C.-300° C.

12. The preparation method according to claim 1, wherein water is added to the mixture of hydrophilic fluorescent vesicles and hydrophobic fluorescent micelles, thereafter, oscillation and standing are performed for separation, and the hydrophilic fluorescent vesicles are obtained from the aqueous phase, while the hydrophobic fluorescent micelles are separated from the oil phase.

13. The preparation method according to claim 12, wherein the volume ratio of the mixture to the water is 0.2:1-10:1.

14. The preparation method according to claim 12, wherein the rate for the oscillation is 10 r/min-1000 r/min.

15. The preparation method according to claim 12, wherein a time for the standing is 0.5 h-100 h.

16. The preparation method according to claim 12, wherein the hydrophilic fluorescent vesicles have a diameter of 1 nm-1000 nm.

17. The preparation method according to claim 12, wherein the fluorescent micelles have a length of 1 nm-2000 nm; the fluorescent micelles have a width of 1 nm-500 nm.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 is a transmission electron microscope (TEM) image of the fluorescent vesicles prepared in Example 1 of the present disclosure.

(2) FIG. 2 is a fluorescence micrograph of the fluorescent vesicles prepared in Example 2 of the present disclosure.

(3) FIG. 3 is a graph showing the fluorescent vesicles prepared in Example 2 of the present disclosure exhibiting blue fluorescence.

(4) FIG. 4 is a graph showing the fluorescent vesicles prepared in Example 2 of the present disclosure exhibiting green fluorescence.

(5) FIG. 5A is a TEM image of the morphology of the FCNs (blue) prepared in Example 7 of the present disclosure.

(6) FIG. 5B is a TEM image of the particle size of the FCNs (blue) prepared in Example 7 of the present disclosure.

(7) FIG. 5C is a particle size distribution diagram of the FCNs (blue) prepared in Example 7 of the present disclosure.

(8) FIG. 6A is a TEM image of the morphology of the FCNs (cyan) prepared in Example 8 of the present disclosure.

(9) FIG. 6B is a TEM image of the particle size of the FCNs (cyan) prepared in Example 8 of the present disclosure.

(10) FIG. 6C is a particle size distribution diagram of the FCNs (cyan) prepared in Example 8 of the present disclosure.

(11) FIG. 7A is a TEM image of the morphology of the FCNs (green) prepared in Example 9 of the present disclosure.

(12) FIG. 7B is a TEM image of the particle size of the FCNs (green) prepared in Example 9 of the present disclosure.

(13) FIG. 7C is a particle size distribution diagram of the FCNs (green) prepared in Example 9 of the present disclosure.

(14) FIG. 8A is a TEM image of the nitrogen-doped FCNs prepared in Example 10 of the present disclosure (scale: 50 nm).

(15) FIG. 8B is a particle size distribution diagram of the nitrogen-doped FCNs prepared in Example 10 of the present disclosure.

(16) FIG. 9A is a TEM image of the nitrogen-doped FCNs prepared in Example 11 of the present disclosure (scale: 50 nm).

(17) FIG. 9B is a particle size distribution diagram of the nitrogen-doped FCNs prepared in Example 11 of the present disclosure.

(18) FIG. 10 is a TEM image of the hydrophilic fluorescent vesicles prepared in Example 12 of the present disclosure (scale: 100 nm).

(19) FIG. 11 is a TEM image of the hydrophobic fluorescent micelles prepared in Example 12 of the present disclosure (scale: 100 nm).

(20) FIG. 12 is a cell imaging diagram of the fluorescent vesicles in Example 12 of the present disclosure.

(21) FIG. 13 is a TEM image of the fluorescent micelles prepared in Example 17 of the present disclosure (scale: 200 nm).

DETAILED DESCRIPTION

(22) The technical solutions of the present disclosure are further illustrated by the specific embodiments below. Those skilled in the art shall understand that the examples are set forth to assist in understanding the present disclosure and should not be regarded as specific limitations to the present disclosure.

Example 1

(23) In this example, fluorescent vesicles were prepared by the following method:

(24) Nonoic acid having a concentration of 60 mM was dissolved in water, sonicated at 100 W for 10 min. And after the solution was uniformly mixed, a reaction was carried out at a stirring rate of 200 r/min under illumination with a wavelength of 254-1100 nm. After 12 hours of reaction, fluorescent vesicles were obtained.

(25) The prepared vesicles were observed with TEM, as shown in FIG. 1. It can be seen that the vesicles have a regular shape and are stable and uniform.

Example 2

(26) In this example, fluorescent vesicles were prepared by the following method:

(27) 2-oxooctanoic acid having a concentration of 200 mM was dissolved in a mixed solvent of water and ethanol, wherein the mass fraction of ethanol was 50%. Then a phosphate buffer (PBS) was added to adjust the pH of the solution to 8, and a photosensitizer was added. After the solution was uniformly mixed, a reaction was carried out at a stirring rate of 300 r/min under illumination with a wavelength of 700 nm. After 16 hours of reaction, fluorescent vesicles were obtained.

(28) The prepared vesicles were observed with TEM, as shown in FIG. 2. It can be seen that the vesicles have a regular shape and are stable and uniform. The prepared fluorescent vesicles were observed by fluorescence microscopy, as shown in FIG. 3 and FIG. 4. It can be observed that the fluorescent vesicles in FIG. 3 exhibit blue color, and the fluorescent vesicles in FIG. 4 exhibit green color and the fluorescence performance is stable.

Example 3

(29) In this example, fluorescent vesicles were prepared by the following method:

(30) Nonoic acid having a concentration of 50 mM was dissolved in a mixed solvent of water and acetonitrile, wherein the volume fraction of acetonitrile was 50%. Then a PBS was added to adjust the pH of the solution to 5. After the solution was uniformly mixed, a reaction was carried out at a stirring rate of 300 r/min under illumination with a wavelength of 180 nm. After 48 hours of reaction, fluorescent vesicles were obtained.

Example 4

(31) In this example, fluorescent vesicles were prepared by the following method:

(32) Cetylic acid having a concentration of 1 M was dissolved in a mixed solvent of water and ethylene glycol, wherein the volume fraction of ethylene glycol was 50%. Then a carbonate buffer was added to adjust the pH of the solution to 6. After the solution was uniformly mixed, a reaction was carried out at a stirring rate of 300 r/min under illumination with a wavelength of 200 nm. After 0.5 hours of reaction, fluorescent vesicles were obtained.

Example 5

(33) In this example, fluorescent vesicles were prepared by the following method:

(34) Linoleic acid having a concentration of 2 mM was dissolved in water, then a formate buffer was added to adjust the pH of the solution to 1. After the solution was uniformly mixed, a reaction was carried out at a stirring rate of 300 r/min under illumination with a wavelength of 313 nm. After 48 hours of reaction, fluorescent vesicles were obtained.

Example 6

(35) In this example, fluorescent vesicles were prepared by the following method:

(36) Oleic acid having a concentration of 20 mM was dissolved in water to obtain a solution with a pH of 7. After the solution was uniformly mixed, a reaction was carried out under illumination with a wavelength of 254 nm. After 10 hours of reaction, fluorescent vesicles were obtained.

Comparison Example 1

(37) Saturated aliphatic acid having a concentration of 60 mM was dissolved in water to obtain a solution with a pH of 7. After the solution was uniformly mixed, a reaction was carried out at a temperature of 50° C. After 12 hours of reaction, fluorescent vesicles were obtained.

Comparison Example 2

(38) Saturated aliphatic acid having a concentration of 20 mM was dissolved in 100% methanol to obtain a solution with a pH of 7. After the solution was uniformly mixed, a reaction was carried out at a temperature of 50° C. After 12 hours of reaction, fluorescent vesicles were obtained.

(39) It can be seen from the comparisons between Examples 1-6 and Comparative Examples 1-2 that if the reaction is not carried out under illumination, fluorescent vesicles cannot be prepared, which proves that illumination is a prerequisite for the formation of the fluorescent vesicles. Meanwhile, if the supplementary solvent content (e.g., methanol content) of the reaction is too high, since it destroys the force between the amphiphilic molecules, the fluorescent vesicles cannot be formed even under illumination.

(40) The preparation method of the fluorescent vesicles provided by the present disclosure is simple, in which the fluorescent vesicles can be obtained only by one step reaction, and the reaction conditions are mild, green and environmentally friendly.

Example 7

(41) In this example, FCNs were prepared by the following method:

(42) Octanoic acid solution having a concentration of 100 mM and citric acid having a concentration of 0.5 M were dissolved in water, and a PBS having a concentration of 0.5 mM was added to adjust the pH of the solution to 7. The solution was uniformly mixed and then subjected to a reaction under illumination with a wavelength of 254-1100 nm and stirring at a rate of 200 r/min. After 12 h of reaction, vesicle-encapsulated FCNs were obtained, then sodium chloride was added, and the vesicles were destroyed to obtain FCNs by separation.

(43) The prepared FCNs were observed by TEM as shown in FIG. 5A, and the particle size diagram was obtained as shown in FIG. 5B, and the particle size distribution diagram is shown in FIG. 5C.

(44) As can be seen from FIG. 5A, the FCNs emit blue fluorescence. As can be seen from FIG. 5B, the FCNs have a particle size of 0.21 nm, and it can be concluded from the particle size distribution diagram in FIG. 5C that the average particle size is 1.6 nm.

Example 8

(45) In this example, FCNs were prepared by the following method:

(46) 2-oxooctanoic acid having a concentration of 200 mM and n-hexane having a concentration of 1 M were dissolved in a mixed solvent of water and ethanol, wherein the volume fraction of ethanol is 50%. And an acetate buffer having a concentration of 0.2 mM was added to adjust the pH of the solution to 5, and a photosensitizer was added. The solution was uniformly mixed and then subjected to a reaction under illumination with a wavelength of 800 nm and stirring at a rate of 300 r/min. After 8 h of reaction, vesicle-encapsulated FCNs were obtained, and FCNs were obtained by destroying the vesicles after standing for 5 days.

(47) The prepared FCNs were observed by TEM as shown in FIG. 6A, and the particle size diagram was obtained as shown in FIG. 6B, and the particle size distribution diagram is shown in FIG. 6C.

(48) As can be seen from FIG. 6A, the FCNs emit cyan fluorescence. As can be seen from FIG. 6B, the FCNs have a particle size of 0.21 nm, and it can be concluded from the particle size distribution diagram in FIG. 6C that the average particle size is 1.6 nm.

Example 9

(49) In this example, FCNs were prepared by the following method:

(50) Octadecanoic acid having a concentration of 1 M and oleic acid having a concentration of 5 M were dissolved in a mixed solvent of water and acetonitrile, wherein the volume fraction of acetonitrile is 90%. And a formate buffer having a concentration of 0.5 M was added to adjust the pH of the solution to 1, and a photosensitizer was added. The solution was uniformly mixed and then subjected to a reaction under illumination with a wavelength of 600 nm and stirring at a rate of 10 r/min. After 48 h of reaction, vesicle-encapsulated FCNs were obtained, then the vesicles were destroyed to obtain FCNs by centrifugation.

(51) The prepared FCNs were observed by TEM as shown in FIG. 7A, and the particle size diagram was obtained as shown in FIG. 7B, and the particle size distribution diagram is shown in FIG. 7C.

(52) As can be seen from FIG. 7A, the FCNs emit green fluorescence. As can be seen from FIG. 7B, the FCNs have a particle size of 0.21 nm, and it can be concluded from the particle size distribution diagram in FIG. 7C that the average particle size is 1.59 nm.

Example 10

(53) In this example, nitrogen-doped FCNs were prepared by the following method:

(54) A solution of nonyl amine having a concentration of 60 mM was dispersed in water, and ultrasonically dispersed for 10 min, then stirred for 10 min. After the solution was mixed evenly, it was subjected to a reaction under illumination with a wavelength of 254 nm-1100 nm and stirring at a rate of 200 r/min. After 12 h of reaction, vesicle-encapsulated FCNs were obtained, and purified FCNs were obtained through extraction with n-hexane and chromatographic column separation.

(55) The prepared FCNs were observed by TEM as shown in FIG. 8A, and the particle size distribution diagram is shown in FIG. 8B.

(56) As can be seen from FIG. 8A, the FCNs are approximately spherical, in which the illustration in the upper right corner is a magnified view of the particles; and as can be seen from FIG. 8B, their average particle diameter is 4.10 nm.

Example 11

(57) In this example, FCNs were prepared by the following method:

(58) A solution of nonaldehyde having a concentration of 60 mM was dispersed in water, and ultrasonically dispersed for 10 min, then stirred for 10 min. After the solution was mixed evenly, it was subjected to a reaction under illumination with a wavelength of 254 nm-1100 nm and stirring at a rate of 200 r/min. After 12 h of reaction, vesicle-encapsulated FCNs were obtained, and purified FCNs were obtained through extraction with n-hexane and chromatographic column separation.

(59) The prepared FCNs were observed by TEM as shown in FIG. 9A, and the particle size distribution diagram is shown in FIG. 9B.

(60) As can be seen from FIG. 9A, the FCNs are approximately spherical; and as can be seen from FIG. 9B, their average particle diameter is 3.71 nm.

Comparison Example 3

(61) In this comparison example, inorganic nanocrystalline vesicle-like microspheres were prepared as in Comparison Example 1 of the method disclosed in CN103920433A as a comparison, and the specific method is as follows:

(62) At room temperature, 50 μL of 7-(12-mercapto dodecyloxy)-2H-benzopyran-2-one in toluene at a concentration of 4 mM was added to gold nanoparticles (having a particle size of 3 nm) modified with oleylamine molecules on the surface in toluene, in which the gold nanoparticles had a mass of 1 mg and the toluene solution had a volume of 4 mL. After the mixture was ultrasound treated for 30 min, it was centrifugal washed twice with about 30 mL of ethanol. The ratio of surface mercaptan to oleylamine was 1:3 as determined by XPS. The resulting solid was dispersed in 400 μL of toluene and then homogenized into 3.6 mL of acetone. The mixture was immediately illuminated with ultraviolet light having a wavelength of 300-400 nm in the air for about 30 minutes while condensed water was introduced to maintain the system at room temperature to obtain vesicle-like microspheres of gold nanocrystals.

Comparison Example 4

(63) In the present comparison example, the nanoparticles were prepared by the method disclosed in CN104327851B, and the specific method is as follows:

(64) 0.6 g of water-soluble carbon nano-dots, 4 g of anhydrous potassium carbonate (Tianjin Guangfu Fine Chemical Research Institute), 0.4 g of potassium iodide (Tianjin Sailboat Chemical Reagent Technology Co., Ltd.), 60 mL of N, N-dimethyl formamide (Xilong Chemical Co., Ltd.), 2.4 mL of bromobutane (Tianjin Guangfu Fine Chemical Research Institute) were weighed to blend in a 250 mL Erlenmeyer flask and heated to reflux at 180° C. for 12 h. After the reaction is completed, the reacted solution was suction filtered twice with a suction filtration device, and then distilled under reduced pressure at 150° C. until the solvent is completely evaporated. The obtained solid was dissolved in 20 mL of toluene (lipophilic carbon nanodots and amphiphilic carbon nanodots were all dissolved in toluene); and the toluene solution in which carbon nanodots were dissolved was centrifuged at high speed to obtain amphiphilic carbon nanodots.

(65) It can be seen from the comparisons of Examples 7-11 and Comparison Examples 3-4 that the preparation method of FCNs provided by the present disclosure is simple, in which the FCNs can be prepared by only one step of reaction, without additional addition of prepared nanoparticles. It also has mild reaction conditions, which reduces the energy consumption of the reaction. However, the carbon nanomaterials prepared in the comparison examples need complicated reaction steps and high energy consumption, which is unfavorable to application.

Example 12

(66) In this example, a mixture of fluorescent vesicles and fluorescent micelles was prepared by the following method:

(67) (1) nonoic acid and water were mixed at a stirring speed of 100 rpm for 5 min to obtain an aqueous solution of nonoic acid at a concentration of 120 mM, followed by an illumination pretreatment at a wavelength of 254-1100 nm for 5 h, and a reaction was carried out under stirring with a stirring speed of 500 rpm and a stirring time of 5 h. And the emulsion obtained after the illumination was then rotary evaporated at a rotary evaporation temperature of 80° C. for 2 h. Then water was added to conduct oscillation and stationary separation, wherein the ratio (volume ratio) of the added water to the rotary evaporated product was 2:1, the oscillation speed was 100 rpm, the oscillation time was 1 min, and the standing time was 20 h. And FCNs-modified hydrophilic fluorescent vesicles were obtained from the water phase, while FCNs-modified hydrophobic fluorescent micelles were obtained from the oil phase by separation.

(68) The above prepared hydrophilic fluorescent vesicles and hydrophobic fluorescent micelles were observed with TEM, and the specific results obtained are shown in FIG. 10 and FIG. 11. As can be seen from FIG. 10, the obtained hydrophilic fluorescent vesicles are evenly distributed and have a diameter distribution of 20 nm-80 nm, and the hydrophobic fluorescent micelles in FIG. 11 have a length distribution of 100 nm-280 nm and a width distribution of 18 nm-70 nm.

(69) The above prepared product was subjected to an imaging result test, as shown in FIG. 12, and it was found that a good imaging effect can be produced.

Example 13

(70) In this example, a mixture of fluorescent vesicles and fluorescent micelles was prepared by the following method:

(71) (1) octanoic acid and water were mixed at a stirring speed of 1000 rpm for 1 min to obtain an aqueous solution of octanoic acid at a concentration of 140 mM, followed by an illumination pretreatment at a wavelength of 313 nm for 12 h, and a reaction was carried out under stirring with a stirring speed of 800 rpm and a stirring time of 11 h. After the reaction was finished, no separation was carried out, and vacuum distillation was conducted at a temperature of 100° C. for 3 h. Then water was added to conduct oscillation and stationary separation, wherein the ratio (volume ratio) of the added water to the distilled product was 4:1, the oscillation speed was 200 rpm, the oscillation time was 6 h, and the standing time was 20 h. And hydrophilic fluorescent vesicles were obtained from the water phase, while FCNs-modified hydrophobic fluorescent micelles were obtained from the oil phase by separation.

(72) The obtained hydrophilic fluorescent vesicles have a diameter distribution of 10 nm-300 nm, and the hydrophobic fluorescent micelles have a length distribution of 20 nm-500 nm and a width distribution of 20 nm-200 nm.

Example 14

(73) In this example, a mixture of fluorescent vesicles and fluorescent micelles was prepared by the following method:

(74) (1) 2-oxooctanoic acid and water were mixed at a stirring speed of 100 rpm for 5 min to obtain an aqueous solution of 2-oxooctanoic acid at a concentration of 120 mM, followed by an illumination pretreatment at a wavelength of 300 nm for 5 h, and a reaction was carried out under stirring with a stirring speed of 500 rpm for 5 h. After the reaction was finished, no separation was carried out, and rotary evaporation was conducted at a temperature of 120° C. for 2 h. Then water was added to conduct oscillation and stationary separation, wherein the ratio (volume ratio) of the added water to the rotary evaporated product was 1:1, the oscillation speed was 100 rpm, the oscillation time was 6 h, and the standing time was 20 h. And the hydrophilic fluorescent vesicles were obtained from the water phase, while FCNs-modified hydrophobic fluorescent micelles were obtained from the oil phase by separation.

(75) The obtained hydrophilic fluorescent vesicles have a diameter distribution of 15 nm-200 nm, and the hydrophobic fluorescent micelles have a length distribution of 90 nm-300 nm and a width distribution of 10 nm-150 nm.

Example 15

(76) In this example, a mixture of fluorescent vesicles and fluorescent micelles was prepared by the following method:

(77) (1) sphingomyelin and water were mixed at a stirring speed of 10 rpm for 60 min to obtain an aqueous solution of sphingomyelin at a concentration of 0.001 mM, followed by an illumination pretreatment at a wavelength of 200 nm for 48 h, and a reaction was carried out under stirring with a stirring speed of 20 rpm for 48 h. And the reaction solution obtained after the illumination was then rotary evaporated at a rotary evaporation temperature of 80° C. and a vacuum degree of −0.1 MPa for 48 h. Then water was added to conduct oscillation and stationary separation, wherein the ratio (volume ratio) of the added water to the rotary evaporated product was 0.2:1, the oscillation speed was 10 rpm, the oscillation time was 6 h, and the standing time was 0.5 h. And the hydrophilic fluorescent vesicles were obtained from the water phase, while FCNs-modified hydrophobic fluorescent micelles were obtained from the oil phase by separation.

(78) The obtained hydrophilic fluorescent vesicles have a diameter distribution of 5 nm-1000 nm, and the hydrophobic fluorescent micelles have a length distribution of 2 nm-1000 nm and a width distribution of 2 nm-500 nm.

Example 16

(79) In this example, a mixture of fluorescent vesicles and fluorescent micelles was prepared by the following method:

(80) (1) polyacrylamide and water were mixed at a stirring speed of 10 rpm for 60 min to obtain an aqueous solution of polyacrylamide at a concentration of 6000 mM, followed by an illumination pretreatment at a wavelength of 313 nm for 0.1 h, and a reaction was carried out under stirring with a stirring speed of 1000 rpm and a stirring time of 0.1 h. After the reaction was finished, no separation was carried out, and rotary evaporation was conducted at a temperature of 120° C. for 0.1 h. Then water was added to conduct oscillation and stationary separation, wherein the ratio (volume ratio) of the added water to the rotary evaporated product was 10:1, the oscillation speed was 1000 rpm, the oscillation time was 6 h, and the standing time was 48 h. And the hydrophilic fluorescent vesicles were obtained from the water phase, while FCNs-modified hydrophobic fluorescent micelles were obtained from the oil phase by separation.

(81) The obtained hydrophilic fluorescent vesicles have a diameter distribution of 10 nm-1000 nm, and the hydrophobic fluorescent micelles have a length distribution of 2 nm-200 nm and a width distribution of 1 nm-1000 nm.

Example 17

(82) In this example, fluorescent micelles were prepared by the following method:

(83) Nonoic acid and water were mixed at a stirring speed of 100 rpm for 5 min to obtain an aqueous solution of nonoic acid at a concentration of 60 mM, followed by rotary evaporation at a temperature of 50° C. for 2 h. After the reaction was finished, fluorescent micelles were obtained without any separation, wherein the binding efficiency of FCNs with micelles is 100%.

(84) The fluorescent micelles prepared in Example 17 were characterized by TEM, and the specific results are shown in FIG. 13. It can be seen from FIG. 13 that the prepared fluorescent micelles have a worm-like shape and are regular, with a length distribution of 100 nm-280 nm and a width distribution of 18 nm-70 nm.

Example 18

(85) In this example, fluorescent micelles were prepared by the following method:

(86) poly(ether-ketone) and water were mixed at a stirring speed of 600 rpm for a stirring time of 15 min to obtain an aqueous solution of poly(ether-ketone) at a concentration of 5 mM, followed by vacuum distillation at a temperature of 120° C. for 48 h. After the reaction was finished, fluorescent micelles were directly obtained without any separation, wherein the binding efficiency of FCNs with micelles is 80%.

Example 19

(87) In this example, fluorescent micelles were prepared by the following method:

(88) Polyacrylamide and water were mixed at a stirring speed of 10 rpm for 60 min to obtain an aqueous solution of polyacrylamide at a concentration of 1000 mM, followed by rotary evaporation at a temperature of 120° C. for 0.1 h. After the reaction was finished, fluorescent micelles were directly obtained without any separation, wherein the binding efficiency of FCNs with micelles is 90%.

Example 20

(89) In this example, fluorescent micelles were prepared by the following method:

(90) 2-oxooctanoic acid and water were mixed at a stirring speed of 100 rpm for 5 min to obtain an aqueous solution of 2-oxooctanoic acid at a concentration of 10 mM, followed by rotary evaporation at a temperature of 50° C. for 15 h. After the reaction was finished, fluorescent micelles were directly obtained without any separation, wherein the binding efficiency of FCNs with micelles is 99%.

Example 21

(91) In this example, fluorescent micelles were prepared by the following method:

(92) Dimethyl distearylammonium chloride and water were mixed at a stirring speed of 1000 rpm for 1 min to obtain an aqueous solution of arachidonic acid at a concentration of 240 mM, followed by atmospheric distillation at a temperature of 130° C. for 0.6 h. After the reaction was finished, fluorescent micelles were obtained without any separation, wherein the binding efficiency of FCNs with micelles is 98%.

Example 22

(93) The only difference between the present example and Example 17 is that, nonoic acid is replaced with tetradecanoic acid, while the remaining operations of the preparation method are the same as that in Example 17. The fluorescent micelles were prepared, wherein the binding efficiency of FCNs with micelles is 90%.

Example 23

(94) The only difference between the present example and Example 17 is that, nonoic acid is replaced with a mixture of nonoic acid and cetylic acid, while the remaining operations of the preparation method are the same as that in Example 17. The fluorescent micelles were prepared, wherein the binding efficiency of FCNs with micelles is 94%.

Example 24

(95) The only difference between the present example and Example 17 is that, the concentration of the prepared aqueous solution of nonoic acid was 1 mM, and the fluorescent micelles were prepared after 65 h, wherein the binding efficiency of FCNs with micelles is (100%).

Example 25

(96) The only difference between the present example and Example 17 is that, the concentration of the prepared aqueous solution of nonoic acid was 1010 mM, and the fluorescent micelles were prepared after 0.1 h. The yield of Example 25 was calculated, and it was found that the binding efficiency of FCNs with micelles decreased to only 78%.

(97) The fluorescent micelles prepared in Examples 17-25 were subjected to stability test. “Standing Time (month)” in Table 1 means that the fluorescent micelles were still stable when the fluorescent micelles were allowed to stand for a certain number of months. The specific method is directly observing the shape of the fluorescent micelles and their binding rate by TEM). The resulting specific data are shown in Table 1 below:

(98) TABLE-US-00001 TABLE 1 Examples Standing Time 17 10 18 8.2 19 7.9 20 9.8 21 9.1 22 8.2 23 9.0 24 9.3 25 9.2

(99) It can be found from the results of Examples 17-23 that the fluorescent micelles prepared by the preparation method provided by the present disclosure have high stability. Except for Examples 18-19, the fluorescent micelles of the remaining examples are stable after standing for 9-10 months, while nonoic acid, 2-oxooctanoic acid, dimethyl distearylammonium chloride and linoleic acid have higher stability and can allow standing for a longer time as compared to other amphiphilic molecules.

(100) The applicant claims that the present disclosure illustrates the preparation methods and applications of the fluorescent nanomaterials of the present disclosure by the above examples, however, the present disclosure is not limited to the above process steps, that is, it does not mean that the present disclosure must rely on the above process steps to be implemented. It will be apparent to those skilled in the art that any modifications of the present disclosure, equivalent substitutions of the materials selected for the present disclosure, and additions of auxiliary ingredients, selections of the specific means and the like, are all within the protection and disclosure scopes of the present disclosure.