CN108034419A - A kind of water solubility full-inorganic perovskite quantum dot and preparation method thereof - Google Patents

Abstract

The invention discloses a water-soluble all-inorganic perovskite quantum dot and a preparation method thereof. The water-soluble all-inorganic perovskite quantum dot has a micellar structure, and its inner layer is an all-inorganic perovskite quantum dot. The outer layer is an amphiphilic phospholipid, and the inner and outer layers are connected by hydrophilic and hydrophobic interactions. The preparation method is as follows: 1) preparing an all-inorganic perovskite quantum dot toluene solution, 2) adding an all-inorganic perovskite quantum dot toluene The solution is uniformly mixed with the amphiphilic phospholipid chloroform solution, and dissolved in ultrapure water after removing the organic solvent to obtain water-soluble all-inorganic perovskite quantum dots. The invention utilizes biocompatible phospholipids to disperse oil-soluble all-inorganic perovskite quantum dots in water, and realizes the fluorescence emission of all-inorganic perovskite quantum dots in water for more than 10 days, and overcomes the problem caused by perovskite quantum dots. Bioimaging limitations caused by easy hydrolysis of dots in water.

Description

A kind of water-soluble all-inorganic perovskite quantum dot and preparation method thereof

technical field

The invention relates to a water-soluble all-inorganic perovskite quantum dot and a preparation method thereof, belonging to the fields of nanomaterials and fluorescence analysis.

Background technique

Quantum dots (quantum dots, QDs), also known as semiconductor nanocrystals, refer to semiconductor materials that reach a certain critical size (exciton Bohr radius) in three-dimensional space and have quantum confinement effects. As a new type of inorganic fluorescent probe, quantum dots have many unique properties, which can effectively overcome some fatal weaknesses of organic fluorescent dyes and fluorescent proteins, mainly as follows: (1) wide excitation spectrum and continuous distribution; (2) The emission spectrum is narrow, usually the full width at half maximum is 25-35nm, and the distribution is symmetrical; (3) the emission spectrum is adjustable within the range of 400nm-1350nm; (4) the fluorescence quantum efficiency is relatively high. Compared with traditional fluorescent dyes, depending on the material, a variety of excitation lights are required to be excited, and the emission spectrum is wide and the overlap phenomenon is serious. Quantum dots can realize multi-wavelength emission at an excitation wavelength, and the emission spectrum overlaps. Inconspicuous, giving it potential for multicolor labeling and detection of multicomponent biological samples.

As a semiconductor material, all-inorganic perovskite quantum dots have the advantages of simple synthesis, narrow emission peak (12-42nm half-maximum width), high fluorescence quantum efficiency (up to 90%), and adjustable luminescence peak position (controlling The types and proportions of halogen elements, and the adjustment of the synthesis temperature of quantum dots to adjust the particle size of quantum dots) and other characteristics, it has a huge advantage in biological imaging, but the poor water stability limits its application in biology, therefore, it is urgent A method for preparing water-soluble all-inorganic perovskite quantum dots is needed to solve the above problems.

Phospholipid, one of the components of biological membranes, has a hydrophilic head and a hydrophobic tail, which can easily form structures such as liposomes and micelles, and is used to carry various hydrophilic and hydrophobic And amphiphilic substances, phospholipid molecules wrapped on the surface of all-inorganic perovskite quantum dots can effectively disperse oil-soluble all-inorganic perovskite quantum dots in water, prevent the hydrolysis of all-inorganic perovskite quantum dots, and improve its stability and biocompatibility, reducing its biotoxicity.

Contents of the invention

Technical problem: The purpose of the present invention is to provide a water-soluble all-inorganic perovskite quantum dot and its preparation method, improve the stability of all-inorganic perovskite quantum dots in water, and realize water-soluble all-inorganic perovskite quantum dots , and the preparation method is simple to operate, good in repeatability and high in biocompatibility.

Technical content: The present invention provides a water-soluble all-inorganic perovskite quantum dot, the water-soluble all-inorganic perovskite quantum dot has a micellar structure, and its inner layer is an all-inorganic perovskite quantum dot CsPbX ₃ Or all inorganic perovskite quantum dots CsPb(Br _n A _1-n ) ₃ , X represents one of Cl, Br or I, A represents one of Cl or I, 0<n<1, the outer layer It is an amphiphilic phospholipid, and the inner and outer layers are connected by hydrophilic and hydrophobic interactions.

in:

The water-soluble all-inorganic perovskite quantum dot is a micellar structure, and its inner layer is all-inorganic perovskite quantum dot CsPbX ₃ and oil-soluble nanoparticles or all-inorganic perovskite quantum dot CsPb(Br _n A _{1 -n} ) ₃ and oil-soluble nanoparticles, X represents one of Cl, Br or I, A represents one of Cl or I, 0<n<1, the outer layer is amphiphilic phospholipid, and the inner and outer layers Linked by hydrophilic and hydrophobic interactions.

The amphipathic phospholipid is one of dipalmitoylphosphatidylcholine, soybean lecithin or distearoylphosphatidylcholine.

The weight mixing ratio of the all-inorganic perovskite quantum dot CsPbX ₃ or the all-inorganic perovskite quantum dot CsPb(Br _n A _1-n ) ₃ to the amphiphilic phospholipid is 1-1.35:54.

The weight mixing ratio of the all-inorganic perovskite quantum dots CsPbX ₃ or all-inorganic perovskite quantum dots CsPb(Br _n A _1-n ) ₃ with oil-soluble nanoparticles and amphiphilic phospholipids is 1 to 1.35: 1～1.35:54.

The present invention also provides a method for preparing water-soluble all-inorganic perovskite quantum dots, the method comprising the following steps:

1) Preparation of all-inorganic perovskite quantum dots CsPbX ₃ or all-inorganic perovskite quantum dots CsPb(Br _n A _1-n ) ₃ : Dissolve PbX ₂ powder and CsX powder according to the molar ratio of each element in the molecular formula CsPbX ₃ Mix solution I in dimethyl sulfoxide, or dissolve PbBr ₂ powder, PbA ₂ powder, CsBr powder and CsA powder in dimethyl sulfoxide according to the molar ratio of each element in _the molecular formula CsPb(Br _n A _1-n ) Mixed solution II was obtained in sulfoxide, and then oleic acid and oleylamine were added to mixed solution I or mixed solution II, and the precursor solution was obtained by ultrasonication until clarified, and then the precursor solution was added to toluene to obtain all-inorganic perovskite quantum dots Toluene solution of CsPbX ₃ or all-inorganic perovskite quantum dot CsPb(Br _n A _1-n ) ₃ toluene solution;

2) Preparation of water-soluble all-inorganic perovskite quantum dots: proportionally mix the toluene solution of all-inorganic perovskite quantum dots CsPbX ₃ or the toluene solution of all-inorganic perovskite quantum dots CsPb(Br _n A _1-n ) ₃ After mixing evenly with amphiphilic phospholipid chloroform solution and oil-soluble nanoparticle chloroform solution, the organic solvent is removed to form a uniform film, and then the film is dissolved in ultrapure water to obtain water-soluble all-inorganic perovskite quantum dots.

in:

Step 1) The concentration of PbX in the mixed solution _I is 0.4mM～1mM, and the concentration of PbA in the mixed solution II is 0.2mM～0.5mM _; Adding oleic acid and oleylamine to solution II refers to mixing solution I or mixed solution II according to the volume ratio: oleic acid: oleylamine is 10-30: 1-6: 0.5-0.8 and adding oleic acid and oleylamine to the mixed solution In I or mixed solution II; step 1) adding the precursor solution into toluene, the volume ratio of toluene to precursor solution is 1-100:1.

Adding the precursor solution to toluene in step 1) refers to adding the precursor solution to toluene at a temperature of 10-40° C. and a stirring rate of 1000 rpm to 1500 rpm.

The amphiphilic phospholipid chloroform solution described in step 2) is prepared by adding amphiphilic phospholipid powder into chloroform, and its concentration is 10-20 mg/mL.

Step 2) the removal of the organic solvent to form a uniform film refers to the removal of the organic solvent under reduced pressure on a rotary evaporator.

Step 2) dissolving the film in ultrapure water to obtain water-soluble all-inorganic perovskite quantum dots refers to dissolving the film in ultrapure water, further centrifuging, and then dissolving in ultrapure water for purification. Water-soluble all-inorganic perovskite quantum dots were obtained.

Beneficial effect: compared with the prior art, the present invention has the following advantages:

1) The present invention uses phospholipid encapsulation technology to coat the surface of oil-soluble all-inorganic perovskite quantum dots with a phospholipid film, which improves the water stability of all-inorganic perovskite quantum dots and makes biological applications possible;

2) The present invention improves the biocompatibility of the all-inorganic perovskite quantum dots by utilizing the phospholipid film, reduces the release of toxic elements in the quantum dots, and reduces the biological toxicity of the quantum dots;

3) The invention has simple operation, multiple optional structures and high repeatability, and provides a simple and efficient method for obtaining water-soluble all-inorganic perovskite quantum dots.

Description of drawings

Fig. 1 is the water-soluble all-inorganic _CsPbBr3 perovskite quantum dot prepared by the present invention schematic diagram of the changing trend of fluorescence with time in 11d;

Fig. 2 is a schematic diagram of the change trend of fluorescence with time within 11d of water-soluble all-inorganic CsPbBr ₃ perovskite quantum dots with magnetic separation ability.

Detailed ways

The present invention uses amphiphilic phospholipid molecules as a medium, so that the oil-soluble all-inorganic perovskite quantum dots are evenly dispersed in water, and have the ability of biological application. The present invention will be further described below in conjunction with the accompanying drawings and examples:

Example 1:

A water-soluble all-inorganic perovskite quantum dot, the water-soluble all-inorganic perovskite quantum dot has a micellar structure, the inner layer is all-inorganic perovskite quantum dot CsPbBr ₃ , and the outer layer is amphiphilic phospholipid Dipalmitoylphosphatidylcholine, the inner and outer layers are connected by hydrophilic and hydrophobic interactions, wherein the weight ratio of all-inorganic perovskite quantum dots CsPbBr ₃ and dipalmitoylphosphatidylcholine is 1:54, and its preparation Include the following steps:

Step 1: Take lead bromide powder and cesium bromide powder at a molar ratio of 1:1 and dissolve them in 10 mL of dimethyl sulfoxide, where the concentration of lead bromide is 0.4 mM; then add 1 mL of oleic acid and 0.5 mL of oleylamine to stabilize , sonicated until the solution was clear to obtain a precursor solution; 0.1 mL of the above precursor was slowly added to 10 mL of toluene under vigorous stirring at 30 ° C to obtain all-inorganic CsPbBr ₃ perovskite quantum dots.

Step 2: Take 200 mg of dipalmitoylphosphatidylcholine powder and dissolve it in 20 mL of chloroform to obtain a 10 mg/mL dipalmitoylphosphatidylcholine chloroform solution.

Step 3: In a 100mL single-necked flask, fully mix the all-inorganic CsPbBr ₃ perovskite quantum dot toluene solution and the dipalmitoylphosphatidylcholine chloroform solution at a ratio of 1:54, and evaporate the organic solvent under reduced pressure to obtain a uniform film.

Step 4: After adding deionized water to completely dissolve the film, centrifuge and redisperse in water to obtain water-soluble all-inorganic perovskite quantum dots.

Example 2:

A water-soluble all-inorganic perovskite quantum dot, the water-soluble all-inorganic perovskite quantum dot is a micellar structure, the inner layer is an all-inorganic perovskite quantum dot CsPbBr _1.5 Cl _1.5 , and the outer layer is an amphiphilic The phospholipid dipalmitoylphosphatidylcholine is connected by hydrophilic and hydrophobic interactions between the inner and outer layers, and the weight ratio of all-inorganic perovskite quantum dots CsPbBr _1.5 Cl _1.5 to dipalmitoylphosphatidylcholine is 1.35: 54, its preparation comprises the following steps:

Step 1: Dissolve lead bromide powder, lead chloride powder and cesium bromide powder in 10 mL of dimethyl sulfoxide according to the molar ratio of 0.5:0.5:1, where the concentration of lead chloride is 0.2 mM; then add 2 mL of oil Acid and 0.5mL oleylamine are stable, sonicate until the solution is clear to obtain a precursor solution; slowly add 1mL of the above precursor to 10mL of toluene under vigorous stirring at 30°C to obtain the toluene of all-inorganic perovskite quantum dots CsPbBr _1.5 Cl _1.5 solution.

Step 2: Take 200 mg of dipalmitoylphosphatidylcholine powder and dissolve it in 20 mL of chloroform to obtain a 10 mg/mL dipalmitoylphosphatidylcholine chloroform solution.

Step 3: In a 100mL single-necked flask, fully mix the all-inorganic perovskite quantum dot CsPbBr _1.5 Cl _1.5 toluene solution and the dipalmitoylphosphatidylcholine chloroform solution in a ratio of 1.35:54, and evaporate the organic solvent under reduced pressure to obtain a uniform film.

Step 4: After adding deionized water to dissolve the film completely, centrifuge and redisperse in water.

Example 3:

A water-soluble all-inorganic perovskite quantum dot, the water-soluble all-inorganic perovskite quantum dot is a micellar structure, the inner layer is an all-inorganic perovskite quantum dot CsPbBr _1.5 I _1.5 , and the outer layer is an amphiphilic The phospholipid dipalmitoylphosphatidylcholine is connected by hydrophilic and hydrophobic interactions between the inner and outer layers. The weight ratio of all-inorganic perovskite quantum dots CsPbBr _1.5 I _1.5 to dipalmitoylphosphatidylcholine is 1.2: 54, its preparation comprises the following steps:

Step 1: Dissolve lead bromide powder, lead iodide powder and cesium bromide powder in 10 mL of dimethyl sulfoxide according to the molar ratio of 0.5:0.5:1, where the concentration of lead iodide is 0.5 mM; add 2 mL of oil The acid and 0.5mL oleylamine are stable, and the solution is sonicated until the solution is clear to obtain a precursor solution; 1mL of the above precursor is slowly added to 10mL of toluene under vigorous stirring at 30°C to obtain the toluene of all-inorganic perovskite quantum dots CsPbBr _1.5 I _1.5 solution.

Step 2: Take 200 mg of dipalmitoylphosphatidylcholine powder and dissolve it in 20 mL of chloroform to obtain a 10 mg/mL dipalmitoylphosphatidylcholine chloroform solution.

Step 3: In a 100mL single-necked flask, fully mix the all-inorganic perovskite quantum dot CsPbBr _1.5 I _1.5 toluene solution and the dipalmitoylphosphatidylcholine chloroform solution in a ratio of 1.2:54, and evaporate the organic solvent under reduced pressure to obtain a uniform film.

Step 4: After adding deionized water to dissolve the film completely, centrifuge and redisperse in water.

Example 4:

A water-soluble all-inorganic perovskite quantum dot, the water-soluble all-inorganic perovskite quantum dot has a micellar structure, the inner layer is all-inorganic perovskite quantum dot CsPbBr ₃ , and the outer layer is amphiphilic soybean Phospholipids are connected by hydrophilic and hydrophobic interactions between the inner and outer layers, wherein the weight ratio of all-inorganic perovskite quantum dots CsPbBr ₃ and soybean phospholipids is 1:54, and its preparation includes the following steps:

Step 1: Take lead bromide powder and cesium bromide powder at a molar ratio of 1:1 and dissolve them in 10 mL of dimethyl sulfoxide, where the concentration of lead bromide is 0.6 mM; then add 1 mL of oleic acid and 0.5 mL of oleylamine to stabilize , sonicated until the solution was clear to obtain a precursor solution; 1 mL of the above precursor was slowly added to 1 mL of toluene under vigorous stirring at 30 ° C to obtain all-inorganic CsPbBr ₃ perovskite quantum dots.

Step 2: Take 200 mg of soybean lecithin powder and dissolve it in 20 mL of chloroform to obtain a 10 mg/mL soybean lecithin chloroform solution.

Step 3: In a 100mL single-necked flask, fully mix the all-inorganic CsPbBr ₃ perovskite quantum dot toluene solution and the soybean phospholipid chloroform solution at a ratio of 1:54, and evaporate the organic solvent under reduced pressure to obtain a uniform film.

Step 4: After adding deionized water to dissolve the film completely, centrifuge and redisperse in water.

Example 5:

A water-soluble all-inorganic perovskite quantum dot, the water-soluble all-inorganic perovskite quantum dot has a micellar structure, the inner layer is all-inorganic perovskite quantum dot CsPbBr ₃ , and the outer layer is amphiphilic bismuth Stearoyl phosphatidylcholine, the inner and outer layers are connected by hydrophilic and hydrophobic interactions, wherein the weight ratio of all-inorganic perovskite quantum dots CsPbBr ₃ and distearoylphosphatidylcholine is 1:54, its Preparation includes the following steps:

Step 1: Take lead bromide powder and cesium bromide powder at a molar ratio of 1:1 and dissolve them in 10 mL of dimethyl sulfoxide, where the concentration of lead bromide is 0.8 mM; then add 1 mL of oleic acid and 0.5 mL of oleylamine to stabilize , sonicated until the solution was clear to obtain a precursor solution; 0.1 mL of the above precursor was slowly added to 10 mL of toluene under vigorous stirring at 30 ° C to obtain all-inorganic CsPbBr ₃ perovskite quantum dots.

Step 2: Take 200 mg of distearoylphosphatidylcholine powder and dissolve it in 20 mL of chloroform to obtain a 10 mg/mL distearoylphosphatidylcholine chloroform solution.

Step 3: In a 100mL single-necked flask, fully mix the all-inorganic CsPbBr ₃ perovskite quantum dot toluene solution and the distearoylphosphatidylcholine chloroform solution at a ratio of 1:54, and evaporate the organic solvent under reduced pressure to obtain a uniform film .

Step 4: After adding deionized water to dissolve the film completely, centrifuge and redisperse in water.

Embodiment 6:

A kind of water-soluble all-inorganic perovskite quantum dot, described water-soluble all-inorganic perovskite quantum dot is micellar structure, and its inner layer is all-inorganic perovskite quantum dot CsPbBr ₃ and oil-soluble ferric oxide Nanoparticles, the outer layer is amphiphilic dipalmitoylphosphatidylcholine, and the inner and outer layers are connected by hydrophilic and hydrophobic interactions, including all-inorganic perovskite quantum dots CsPbBr ₃ , oil-soluble ferric oxide nanoparticles, The weight ratio of dipalmitoylphosphatidylcholine is 1:1:54, and its preparation comprises the following steps:

Step 1: Take lead bromide powder and cesium bromide powder at a molar ratio of 1:1, dissolve in 10 mL of dimethyl sulfoxide, where the concentration of lead bromide is 0.4 mM; then add 1 mL of oleic acid and 0.5 mL of oleylamine Stable, sonicate until the solution is clear to obtain a precursor solution; slowly add 1 mL of the above precursor to 1 mL of toluene under vigorous stirring at 30 °C to obtain a toluene solution of all-inorganic perovskite quantum dots CsPbBr ₃ .

Step 2: Take 200 mg of dipalmitoylphosphatidylcholine powder and dissolve it in 20 mL of chloroform to obtain a 10 mg/mL dipalmitoylphosphatidylcholine chloroform solution.

Step 3: Take 200 mg of oil-soluble iron ferric oxide nanoparticles and dissolve them in 20 mL of chloroform to obtain a 10 mg/mL oil-soluble iron ferric oxide nano-particle chloroform solution.

Step 4: In a 100mL single-necked flask, fully mix the all-inorganic perovskite quantum dots CsPbBr ₃ : oil-soluble iron ferric oxide nanoparticles in chloroform: dipalmitoylphosphatidylcholine in chloroform at a ratio of 1:1:54 , the organic solvent was evaporated under reduced pressure to obtain a uniform film.

Step 5: After adding deionized water to dissolve the film completely, centrifuge and redisperse in water.

Embodiment 7:

A kind of water-soluble all-inorganic perovskite quantum dot, described water-soluble all-inorganic perovskite quantum dot is micellar structure, and its inner layer is all-inorganic perovskite quantum dot CsPbBr ₃ and oil-soluble ferric oxide Nanoparticles, the outer layer is amphiphilic dipalmitoylphosphatidylcholine, and the inner and outer layers are connected by hydrophilic and hydrophobic interactions, including all-inorganic perovskite quantum dots CsPbBr ₃ , oil-soluble ferric oxide nanoparticles, The weight ratio of dipalmitoylphosphatidylcholine is 1.35:1:54, and its preparation comprises the following steps:

Step 1: Take lead bromide powder and cesium bromide powder at a molar ratio of 1:1, dissolve in 10 mL of dimethyl sulfoxide, where the concentration of lead bromide is 0.5 mM; then add 1 mL of oleic acid and 0.5 mL of oleylamine Stable, sonicate until the solution is clear to obtain a precursor solution; slowly add 1 mL of the above precursor to 1 mL of toluene under vigorous stirring at 30 °C to obtain a toluene solution of all-inorganic perovskite quantum dots CsPbBr ₃ .

Step 2: Take 200 mg of dipalmitoylphosphatidylcholine powder and dissolve it in 20 mL of chloroform to obtain a 10 mg/mL dipalmitoylphosphatidylcholine chloroform solution.

Step 3: Take 200 mg of oil-soluble iron ferric oxide nanoparticles and dissolve them in 20 mL of chloroform to obtain a 10 mg/mL oil-soluble iron ferric oxide nano-particle chloroform solution.

Step 4: In a 100mL single-necked flask, mix the all-inorganic perovskite quantum dots CsPbBr ₃ : oil-soluble iron ferric oxide nanoparticles in chloroform: dipalmitoylphosphatidylcholine in chloroform at a ratio of 1.35:1:54 , the organic solvent was evaporated under reduced pressure to obtain a uniform film.

Step 5: After adding deionized water to dissolve the film completely, centrifuge and redisperse in water.

Embodiment 8:

A water-soluble all-inorganic perovskite quantum dot, the water-soluble all-inorganic perovskite quantum dot is a micellar structure, and its inner layer is an all-inorganic perovskite quantum dot CsPbBr ₃ and oil-soluble gold nanoparticles, The outer layer is amphiphilic dipalmitoylphosphatidylcholine, and the inner and outer layers are connected by hydrophilic and hydrophobic interactions, in which all-inorganic perovskite quantum dots CsPbBr ₃ , oil-soluble gold nanoparticles, The weight ratio of the base is 1:1:54, and its preparation includes the following steps:

Step 1: Take lead bromide powder and cesium bromide powder at a molar ratio of 1:1, dissolve in 10 mL of dimethyl sulfoxide, where the concentration of lead bromide is 0.7 mM; then add 1 mL of oleic acid and 0.5 mL of oleylamine Stable, sonicate until the solution is clear to obtain a precursor solution; slowly add 1 mL of the above precursor to 1 mL of toluene under vigorous stirring at 30 °C to obtain a toluene solution of all-inorganic perovskite quantum dots CsPbBr ₃ .

Step 2: Take 200 mg of dipalmitoylphosphatidylcholine powder and dissolve it in 20 mL of chloroform to obtain a 10 mg/mL dipalmitoylphosphatidylcholine chloroform solution.

Step 3: Take 200 mg of oil-soluble gold nanoparticles and dissolve them in 20 mL of chloroform to obtain a 10 mg/mL chloroform solution of oil-soluble gold nanoparticles.

Step 4: In a 100mL single-necked flask, fully mix the all-inorganic perovskite quantum dots CsPbBr ₃ : oil-soluble gold nanoparticles in chloroform: dipalmitoylphosphatidylcholine in chloroform in a ratio of 1:1:54, and depressurize The organic solvent was evaporated to obtain a uniform film.

Step 5: After adding deionized water to dissolve the film completely, centrifuge and redisperse in water.

Embodiment 9:

A water-soluble all-inorganic perovskite quantum dot, the water-soluble all-inorganic perovskite quantum dot is a micellar structure, and its inner layer is an all-inorganic perovskite quantum dot CsPbBr ₃ and oil-soluble gold nanoparticles, The outer layer is amphiphilic distearoyl phosphatidylcholine, and the inner and outer layers are connected by hydrophilic and hydrophobic interactions, in which all-inorganic perovskite quantum dots CsPbBr ₃ , oil-soluble gold nanoparticles, The weight ratio of acetylcholine is 1:1.35:54, and its preparation comprises the following steps:

Step 1: Take lead bromide powder and cesium bromide powder at a molar ratio of 1:1, dissolve in 10 mL of dimethyl sulfoxide, where the concentration of lead bromide is 0.4 mM; then add 1 mL of oleic acid and 0.5 mL of oleylamine Stable, sonicate until the solution is clear to obtain a precursor solution; slowly add 1 mL of the above precursor to 1 mL of toluene under vigorous stirring at 30 °C to obtain a toluene solution of all-inorganic perovskite quantum dots CsPbBr ₃ .

Step 2: Take 200 mg of distearoylphosphatidylcholine powder and dissolve it in 20 mL of chloroform to obtain a 10 mg/mL distearoylphosphatidylcholine chloroform solution.

Step 3: Take 200 mg of oil-soluble gold nanoparticles and dissolve them in 20 mL of chloroform to obtain a 10 mg/mL chloroform solution of oil-soluble gold nanoparticles.

Step 4: In a 100mL single-necked flask, the all-inorganic perovskite quantum dots CsPbBr ₃ : oil-soluble gold nanoparticles chloroform solution: distearoylphosphatidylcholine chloroform solution is fully mixed according to the ratio of 1:1.35:54, and the The organic solvent was evaporated under high pressure to obtain a uniform film.

Step 5: After adding deionized water to dissolve the film completely, centrifuge and redisperse in water.

It can be seen from Figure 1 that the all-inorganic perovskite quantum dots coated with phospholipids can achieve fluorescence emission in water for more than 10 days; it can be seen from Figure 2 that functionalized nanoparticles can be simply added to water-soluble all-inorganic calcium Titanium quantum dots, and have long-term fluorescence emission ability.

The above is only a preferred embodiment of the present invention, it should be pointed out that for those of ordinary skill in the art, without departing from the principle of the present invention, some improvements and modifications can also be made, and these improvements and modifications are also possible. It should be regarded as the protection scope of the present invention.

Claims (10)

1. A kind of 1. water solubility full-inorganic perovskite quantum dot, it is characterised in that：The water-soluble full-inorganic perovskite quantum dot For micelle-like structures, its internal layer is full-inorganic perovskite quantum dot CsPbX₃Or full-inorganic perovskite quantum dot CsPb (Br_nA_1-n)₃, X represent Cl, Br or I in one kind, A represent Cl or I in one kind, 0 ＜ n ＜ 1, its outer layer is amphiphilic phosphatide, It is connected between ectonexine by hydrophilic with hydrophobic interaction.
2. A kind of 2. water-soluble full-inorganic perovskite quantum dot as claimed in claim 1, it is characterised in that：The water solubility is complete Inorganic perovskite quantum dot is micelle-like structures, its internal layer is full-inorganic perovskite quantum dot CsPbX₃And oil-soluble nano particles Or full-inorganic perovskite quantum dot CsPb (Br_nA_1-n)₃And oil-soluble nano particles, X represent one kind in Cl, Br or I, A is represented One kind in Cl or I, 0 ＜ n ＜ 1, its outer layer are amphiphilic phosphatide, are connected between ectonexine by hydrophilic with hydrophobic interaction Connect.
3. A kind of 3. water-soluble full-inorganic perovskite quantum dot as claimed in claim 1 or 2, it is characterised in that：The parents Property phosphatide be dipalmitoylphosphatidylcholine, soybean lecithin or distearoyl phosphatidylcholine in one kind.
4. A kind of 4. water-soluble full-inorganic perovskite quantum dot as claimed in claim 1, it is characterised in that：The full-inorganic calcium Titanium ore quantum dot CsPbX₃Or full-inorganic perovskite quantum dot CsPb (Br_nA_1-n)₃Mixing ratio by weight example with amphiphilic phosphatide is 1 ~1.35:54.
5. A kind of 5. water-soluble full-inorganic perovskite quantum dot as claimed in claim 2, it is characterised in that：The full-inorganic calcium Titanium ore quantum dot CsPbX₃Or full-inorganic perovskite quantum dot CsPb (Br_nA_1-n)₃With oil-soluble nano particles, amphiphilic phosphatide three The Mixing ratio by weight example of person is 1~1.35:1~1.35:54.
6. 6. a kind of preparation method of full-inorganic perovskite quantum dot water-soluble as described in claim 1 or 2, its feature exist In：This method comprises the following steps：

   1) full-inorganic perovskite quantum dot CsPbX₃Or full-inorganic perovskite quantum dot CsPb (Br_nA_1-n)₃Preparation：By molecular formula CsPbX₃The molar ratio of middle each element is by PbX₂Powder and CsX powder, which are dissolved in dimethyl sulfoxide (DMSO), obtains mixed solution I, or By molecular formula CsPb (Br_nA_1-n)₃The molar ratio of middle each element is by PbBr₂Powder, PbA₂Powder, CsBr powder and CsA powder are molten Solution obtains mixed solution II in dimethyl sulfoxide (DMSO), backward mixed solution I or mixed solution II in add oleic acid and oleyl amine, surpass Sound to clarification obtains precursor solution, afterwards adds in toluene precursor solution, obtains full-inorganic perovskite quantum dot CsPbX₃Toluene solution or full-inorganic perovskite quantum dot CsPb (Br_nA_1-n)₃Toluene solution；

   2) preparation of water-soluble full-inorganic perovskite quantum dot：In proportion by full-inorganic perovskite quantum dot CsPbX₃Toluene it is molten Liquid or full-inorganic perovskite quantum dot CsPb (Br_nA_1-n)₃Toluene solution and amphiphilic phosphatide chloroformic solution, oil solubility nanometer grain Sub- chloroformic solution after mixing, removes organic solvent and forms uniform film, afterwards by Film Fractionation in ultra-pure water, obtain water Dissolubility full-inorganic perovskite quantum dot.
7. A kind of 7. preparation method of water-soluble full-inorganic perovskite quantum dot as claimed in claim 6, it is characterised in that：Step 1) PbX in the mixed solution I described in₂Concentration be 0.4mM~1mM, PbA in the mixed solution II₂Concentration be 0.2mM ~0.5mM；Oleic acid and oleyl amine are added into mixed solution I or mixed solution II described in step 1), refers to mix according to volume ratio Close solution I or mixed solution II：Oleic acid：Oleyl amine is 10~30：1~6：Oleic acid and oleyl amine are added to mixed solution by 0.5~0.8 I or mixed solution II in；Adding precursor solution in toluene described in step 1), the volume ratio of toluene and precursor solution is 1~100：1.
8. A kind of 8. preparation method of water-soluble full-inorganic perovskite quantum dot as claimed in claim 6, it is characterised in that：Step 2) the amphiphilic phosphatide chloroformic solution described in is added in chloroform by amphiphilic phosphatide powder to be prepared, its concentration is 10~20mg/mL.
9. A kind of 9. preparation method of water-soluble full-inorganic perovskite quantum dot as claimed in claim 6, it is characterised in that：Step 2) the removal organic solvent described in forms uniform film and refers to depressurize removal organic solvent on a rotary evaporator.
10. A kind of 10. preparation method of water-soluble full-inorganic perovskite quantum dot as claimed in claim 6, it is characterised in that：Step It is rapid 2) described in by Film Fractionation in ultra-pure water, obtain water-soluble full-inorganic perovskite quantum dot and refer to Film Fractionation in super After in pure water, further through centrifuging, being re-dissolved in purify in ultra-pure water, water-soluble full-inorganic perovskite quantum dot is obtained.