Preparation of nanospheres and aqueous dispersions of nanospheres based on nonpolar molecules

Abstract

The present application relates to a kind of nanosphere and the preparation of nonpolar molecule-based nanosphere aqueous dispersion, nanosphere is formed by CIAA in aqueous phase by self-assembly;CIAA is by 1 containing hydrophilic functional group subassembly and 1-2 nonpolar restriction subassembly chemical linkage;Subassembly is the group with planar conjugated structure;Nonpolar restriction subassembly is the group with nanometer size three-dimensional structure, or can be in aqueous phase due to hydrophobic effect group shrinks into nanometer size three-dimensional structure;The preparation of dispersion: first, CIAA is dissolved in tetrahydrofuran, forms CIAA / tetrahydrofuran solution, then adds ultrapure water to the solution, obtains colloid, finally removes tetrahydrofuran in colloid by dialysis method, obtains nonpolar molecule-based nanosphere aqueous dispersion with concentration of 0.1-2mg / mL.The preparation process of nonpolar molecule-based nanosphere aqueous dispersion of the present application is simple, and there is no need to have the synthesis of microsphere matrix, but is formed by molecular self-assembly microsphere.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of preparation of nanomicrosphere aqueous dispersion, and relates to a nanomicrosphere and preparation of nanomicrosphere aqueous dispersion based on nonpolar molecules. BACKGROUND

[0002] Nanomicrosphere is a kind of small particle with particle size of 5 nanometers to 1000 microns, which is widely used as liquid crystal spacer, drug carrier, enzyme carrier, etc. There are various methods for preparing nanomicrosphere, and water as a dispersion medium is an important method for preparing nanomicrosphere. Water as a dispersant is low in price, non-polluting to the environment, and green and environmentally friendly. However, in the existing preparation method of nanomicrosphere, an additive (surfactant) is needed to make the molecules stably dispersed in the aqueous phase, and the surfactant often has an amphiphilic structure; or the molecules constituting the nanomicrosphere have an amphiphilic structure (CN201710023290.5 A kind of multi-pyridine naphthalimide fluorescent dendrimer and its preparation method and application; CN201710158228.7 A size-adjustable perylene imide multifunctional nanoparticle and its preparation and application). Especially in the preparation process of hydrophobic nanomicrosphere, the dispersing aid with amphiphilic structure is the key to its stable dispersion in the aqueous phase (CN201810689542.2 A nanomicrosphere based on aggregation-induced emission material and its preparation method and application; CN201110387145.8 A kind of polymerizable fluorescent dye, its preparation method and application; CN201810742582.9 A preparation method of fluorescent magnetic microspheres; CN201310048740.8 Quantum dot nanoparticles containing a hydrophobic interlayer and a preparation method thereof; CN201210436603.7 A method for realizing water phase transfer and cell nucleus targeting of hydrophobic nanoparticles simultaneously). On the other hand, the water phase dispersion of nanoparticles is also an important step for its application, and the nanoparticles composed of amphiphilic molecules are relatively easy to disperse in the aqueous phase (CN201310553560.5 A monomolecular fluorescent polymer micelle and its application as a pH probe; CN201910467076.8 Preparation and application method of light-controlled fluorescent polymer nanoparticles), but the uniform dispersion of hydrophobic nanoparticles in the aqueous phase is more difficult, and the help of the additive is needed, and the existing dispersion method mainly disperses the hydrophobic nanoparticles by adding surfactant (CN201110342740.X A water phase dispersion method of hydrophobic organic dye nanoparticles; CN201110353986.7 A preparation method of water phase dispersion wavelength adjustable dye nanoparticle); or modifies the surface of the hydrophobic nanoparticles (CN201710961337.2 A preparation method of hydrophobic magnetic nanoparticles easy to disperse in water phase).

[0003] In the preparation of the water phase dispersion of the high concentration of the hydrophobic particles, not only the addition of various kinds of stabilizers is needed, but also the mechanical (homogenizer, high speed homogenizer, high pressure homogenizer, ultrasonic, ball mill or medium grinding, etc.) is needed to help the dispersion to form. The dispersion obtained by the above means is emulsified, and the concentration of the dispersion is high.

[0004] The large amount of discharge of the wastewater containing the surfactant not only directly harms the aquatic environment, kills the microorganisms in the environment, and inhibits the degradation of other toxic substances, but also causes the decrease of the dissolved oxygen in the water, especially the surfactant containing nitrogen and phosphorus, which can cause the eutrophication of the water body. When the surfactant in the wastewater entering the sewage treatment plant reaches a certain concentration, it can affect the aeration, sedimentation, sludge nitrification and many other processes. The residual surfactant in the soil has a certain influence on the growth of the soil microorganisms. In addition, the adsorption capacity of some surfactants in the soil is very weak, and the potential harm of the downward migration of the surfactants to pollute the groundwater is also not ignored. While using the chemical surfactant for environmental remediation, the surfactant is inevitably left in the environment. Therefore, the water phase dispersion of the hydrophobic particles without the surfactant needs to be realized for the protection of the environment and the soil. SUMMARY

[0005] The purpose of the present application is to solve the above problems existing in the prior art, and to provide a kind of nanosphere and the preparation of the water phase dispersion of nanosphere based on nonpolar molecules.

[0006] In order to achieve the above purpose, the technical scheme adopted by the present application is as follows:

[0007] A kind of nanosphere is formed by CIAA (cavity induced water phase assembly molecule) in water phase through self-assembly (CIAA can self-assemble in water phase, on the one hand, because the assembly sub of CIAA molecule has strong π-π interaction, the assembly of molecules is driven by π-π interaction, on the other hand, because CIAA molecule is nonpolar, completely hydrophobic, under the hydrophobic effect, CIAA molecule will gather);CIAA is chemically linked by 1 assembly sub containing hydrophilic functional group and 1-2 nonpolar limiting assembly sub, and CIAA is nonpolar;

[0008] The assembly sub is a group with a planar conjugated structure, specifically (naphthalimide group, wherein the hydrophilic functional group is imide functional group)、 (perylenetetracarboxylic acid imide derivative group, wherein the hydrophilic functional group is imide functional group)、 (naphthalimide derivative group, wherein the hydrophilic functional group is imide functional group)

[0009] wherein * is a chemical bonding position;

[0010] The non-polar limiting assembly is a group with a nano-sized three-dimensional structure, or a group capable of being shrunk into a nano-sized three-dimensional structure in an aqueous phase due to a hydrophobic group;

[0011] The group with a nano-sized three-dimensional structure is wherein * is a chemical bonding position, R is an isobutyl group or an isooctyl group, and R1 and R2 are each independently selected from an alkyl chain with less than 20 carbon atoms.

[0012] As a preferred technical solution:

[0013] The group capable of being shrunk into a nano-sized three-dimensional structure in an aqueous phase due to a hydrophobic group is an alkyl chain with more than 6 carbons (because the alkyl chain is hydrophobic, it will be shrunk due to hydrophobic effect in water, and more than 6 carbons can be shrunk into a three-dimensional structure).

[0014] The application further provides a preparation method of the nano-microsphere aqueous dispersion based on non-polar molecules. CIAA is dissolved in tetrahydrofuran (THF, the selected solvent needs to be miscible with water and capable of dissolving CIAA molecules) to form a uniform CIAA / tetrahydrofuran solution, and then ultra-pure water is rapidly (within 5-10 seconds) added to the CIAA / tetrahydrofuran solution to obtain a colloid. Finally, tetrahydrofuran in the colloid is removed by dialysis to obtain the nano-microsphere aqueous dispersion based on non-polar molecules.

[0015] CIAA is self-assembled into nano-microspheres in an aqueous phase; CIAA is chemically bonded by 1 assembly with a hydrophilic functional group and 1-2 non-polar limiting assemblies, and CIAA is non-polar;

[0016] The assembly is

[0017] wherein * is a chemical bonding position; the non-polar limiting assembly is a group with a nano-sized three-dimensional structure, or a group capable of being shrunk into a nano-sized three-dimensional structure in an aqueous phase due to a hydrophobic group;

[0018] The group with a nano-sized three-dimensional structure is wherein * is a chemical bonding position, R is an isobutyl group or an isooctyl group, and R1 and R2 are each independently selected from an alkyl chain with less than 20 carbon atoms.

[0019] The mass volume ratio of CIAA to tetrahydrofuran is 1 mg:1 mL to 10 mg:1 mL, and the volume ratio of CIAA / tetrahydrofuran solution to ultrapure water is 1:5 to 1:10;

[0020] The concentration of the nano-microsphere aqueous phase dispersion based on non-polar molecules is 0.1-2 mg / mL.

[0021] As the preferred technical solution:

[0022] The method described above, wherein tetrahydrofuran is removed from the colloid by dialysis, is specifically as follows: the colloid is transferred to a dialysis bag with a molecular weight cut-off > 500, and the colloid is dialyzed with pure water, wherein the pure water for dialysis is replaced 1.5 h, 4 h, and 8 h after the start of dialysis, respectively. The volume ratio of pure water for dialysis to the dispersion is 2000-4000:11 each time, and the dialysis is terminated after 24 h.

[0023] According to the method described above, the particle size in the aqueous dispersion of nanospheres based on non-polar molecules is 50 to 200 nm, and the polydispersity index is 0.1 to 0.7 (the dispersion index of the nanospheres is small, indicating that the size distribution is relatively uniform). The particle size and polydispersity index are measured by dynamic laser light scattering (DLS) testing method, the test temperature is 25 to 30°C, the test time is 3 to 5 minutes, the Zeta potential is -60 to -40 mV (the Zeta potential less than -40 mV indicates that the microspheres have good stability in the aqueous phase), and the Zeta potential test temperature is 25 to 30°C.

[0024] After the aqueous dispersion of nanospheres based on non-polar molecules of the present invention is placed for 7 to 10 days, the particle size of the microspheres fluctuates within ±5 to ±10 nm of the original size, the polydispersity index fluctuates within ±0.01 to ±0.05 of the original value, and the zeta potential fluctuates within ±2 to ±10 mV of the original value. All numerical fluctuation ranges are within the measurement error, indicating that the microspheres have good stability.

[0025] In the above method, the group that can shrink into a nanometer-sized three-dimensional structure due to hydrophobic interaction in the aqueous phase is an alkyl chain with more than 6 carbon atoms.

[0026] The principles of the present invention are as follows:

[0027] In colloidal particles, CIAA molecules have a large steric hindrance due to the limited assembly, and the molecules do not form continuous π-π stacking, but instead aggregate with oligomers (the number of aggregated molecules is less than 3) as the basic unit. Since the restricted assembler has a three-dimensional structure at the nanometer scale, and the assembler can be regarded as a component structure of a two-dimensional plate-like plane, the restricted assembler and the assembler have three-dimensional and two-dimensional structures in spatial dimensions respectively, so they have shape anisotropy in their arrangement. Therefore, the CIAA molecule has many cavities in the assembly structure. In the nanospheres, the CIAA molecules exist in a loose state, and there are many holes in their arrangement structure. Water molecules enter these holes to form internal water in the nanospheres. There are dynamic hydrogen bonds between the internal water and the bulk water (water in the system other than the internal water) (because hydrogen bonds are non-covalent bonds, which are weak interactions between molecules, and the hydrogen bonds in water are shown in the literature to be dynamic, that is, the hydrogen bonds may be broken the next moment). In the three-dimensional network structure jointly constructed by the internal water and the bulk water, the nanoparticles can stably exist in the aqueous phase for a long time (there is a certain interaction between the internal water and the bulk water, which makes the water form a three-dimensional network, as if the internal water in the nanospheres is framed in a three-dimensional network structure). In the molecular structure of the present invention, the assembly sub-group is introduced into the perylene imide bay position, or the naphthalene imide with a small conjugated area is used, which reduces the interaction between molecules and can be made into a dispersion of higher concentration (up to 2 mg / mL). Wherein, the restricted assembly sub-group mentioned in the present invention is a class of flexible long chains. In the aqueous phase, due to the influence of the hydrophobic effect, the chain segments shrink to form a structure with a three-dimensional nanometer scale. Different from some rigid three-dimensional nanometer-scale substituent structures, this three-dimensional nanometer-scale structure formed by assembly is spontaneously formed, and this structure is not rigid and has a deformable performance within a certain range. At the same time, due to the spontaneous formation, water molecules also participate in its assembly to further stabilize the three-dimensional nanometer-scale structure formed.

[0028] Beneficial effects:

[0029] (1) The existing technology cannot achieve stable dispersion of hydrophobic molecules in water. The present invention achieves the assembly of hydrophobic molecules in the aqueous phase to form a nano-microsphere aqueous phase dispersion with a stable structure;

[0030] (2) The preparation of the aqueous dispersion of nanospheres based on non-polar molecules of the present invention is simple and does not require the synthesis of a microsphere matrix. Instead, the microspheres are formed by molecular self-assembly.

[0031] (3) The present invention does not require the use of surfactants to prepare microspheres, and the microspheres can be stably and evenly dispersed in the aqueous phase for a long time. BRIEF DESCRIPTION OF THE DRAWINGS

[0032] Figure 1Schematic diagram of the internal structure of nanospheres in aqueous dispersion prepared based on non-polar molecules. DETAILED DESCRIPTION

[0033] Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiments are only used to illustrate the present invention and are not used in limiting the scope of the present invention.In addition, should be understood that after reading the content taught by the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms fall equally within the scope limited by the appended claims of the application.

[0034] Figure 1 This is a schematic diagram of the internal structure of nanospheres in the aqueous dispersion of nanospheres prepared based on non-polar molecules. Specifically, the CIAA molecules in the nanospheres exist in an oligomeric state. Due to the presence of cavities in the molecular arrangement structure, the nanoparticles have a large amount of internal water. Due to the dynamic hydrogen bonds between the internal water and the bulk water, the nanoparticles can exist stably in the hydrogen bond network.

[0035] Table 1

[0036]

[0037]

[0038] Table 2

[0039]

[0040] Example 1

[0041] A preparation method of CIAA, comprising the following steps:

[0042] (1) Add 2g of (perylene tetracarboxylic anhydride) and 29.40 mL of concentrated sulfuric acid were stirred at 55° C. for 24 h, and then 0.05 g of iodine was added to the mixture, and stirring was continued for 5 h. Subsequently, 0.58 mL of liquid bromine was added dropwise at a controlled rate of 1 h, and the mixture was heated to 85° C. and stirred for 24 h. Excess bromine was removed by N2 atmosphere, 30.00 mL of ice water was added, the mixture was cooled, filtered, and washed with 18 mL of 86% H2SO4, and then washed with double the amount of ice water to obtain a crude product (2.70 g, 96%). The crude product was recorded as PTCDA-Br without separation and purification and was directly used in the next step of synthesis.

[0043] (2) After adding 0.5 g of the crude PTCDA-Br product prepared above and 15 mL of 1-methyl-2-pyrrolidone (NMP) into a 100 mL three-necked flask, the mixture was stirred at 25°C for 1 h. 0.587 g of 2-ethylhexylamine was then added, followed by 16.80 g of glacial acetic acid. The temperature was raised to 85°C, and the reaction was continued under N2 protection for 7 h. The mixture was cooled to room temperature, 120 mL of methanol was added, and the mixture was stirred overnight. Finally, the mixture was filtered, dried in vacuo, and purified by silica gel (200 mesh) column chromatography to obtain a red solid, which was recorded as 1,7-Br-PDI-EH.

[0044] (3) 100 mg of the isolated 1,7-Br-PDI-EH was added to a round-bottom flask and dissolved in 20 mL of tetrahydrofuran (THF). A magnetic stirrer was added and stirred for 1 h to allow the 1,7-Br-PDI-EH to fully dissolve. Then, 60.8 mg of potassium carbonate and 108.48 mg of 18-crown-6-ether were added, followed by 0.2 g of The reaction was stopped by stirring at room temperature for 2 h, and then water and chloroform were added for extraction after rotary evaporation to obtain a chloroform extract, which was finally purified by column chromatography to obtain the target product, namely CIAA.

[0045] The prepared CIAA is chemically bonded by an assembler containing a hydrophilic functional group and a non-polar restricting assembler, and CIAA is non-polar; among them, the assembler is S-5 in Table 1; the non-polar restricting assembler is Q-1 in Table 2; CIAA can form nanospheres through self-assembly in the aqueous phase.

[0046] Example 2

[0047] A preparation method of CIAA, comprising the following steps:

[0048] (1) 2.00 g of perylene tetracarboxylic anhydride and 29.40 mL of concentrated sulfuric acid were added to a 100 mL three-necked flask in sequence, and the mixture was stirred at 55°C for 24 h. Then, 0.05 g of iodine was added to the mixture, and the stirring was continued for 5 h. Subsequently, 0.58 mL of liquid bromine was added dropwise at a controlled rate of 1 h. The mixture was heated to 85°C and stirred for 24 h. The excess bromine was removed by N2 atmosphere, 30 mL of ice water was added, the mixture was cooled, filtered, and washed with 18 mL of 86% H2SO4 by mass, and then washed with double the amount of ice water to obtain a crude product (2.70 g, 96%). The crude product was not separated or purified and was recorded as PTCDA-Br and used directly in the next step of synthesis.

[0049] (2) Add 0.50 g of the crude PTCDA-Br product prepared above and 15 mL of 1-methyl-2-pyrrolidone to a 100 mL three-necked flask and stir at 25°C for 1 h; then add 0.587 g of 2-ethylhexylamine and 16.8 g of glacial acetic acid, heat to 85°C and continue to react under N2 protection for 7 h; cool to room temperature, add 120 mL of methanol, stir overnight, and finally filter, vacuum dry, and separate and purify by silica gel (200 mesh) column chromatography to obtain a red solid recorded as 1,7-Br-PDI-EH;

[0050] (3) 100 mg of the isolated 1,7-Br-PDI-EH was added to a round-bottom flask and dissolved in 20 mL of tetrahydrofuran. A magnetic stirrer was added and stirred for 1 h to allow the 1,7-Br-PDI-EH to fully dissolve. 60.8 mg of potassium carbonate and 108.48 mg of 18-crown-6-ether were then added, followed by 0.45 g of The reaction was stopped by stirring at room temperature for 2 h, and then water and chloroform were added for extraction after rotary evaporation to obtain a chloroform extract, which was finally purified by column chromatography to obtain the target product, namely CIAA.

[0051] The prepared CIAA is composed of one assembler containing a hydrophilic functional group and two non-polar restricting assemblers chemically bonded together, and CIAA is non-polar; among them, the assembler is S-3 in Table 1; the non-polar restricting assembler is Q-2 in Table 2; CIAA can form nanospheres through self-assembly in the aqueous phase.

[0052] Example 3

[0053] A preparation method of CIAA, comprising the following steps:

[0054] 0.11g C 60 -COOH, 0.024g (Naphthalene tetracarboxylic anhydride), 1g imidazole and 4ml o-dichlorobenzene (ODCB) were placed in a round-bottom flask, condensed and refluxed, heated in an oil bath at 140°C under argon atmosphere, and stirred for 6h. After cooling, the mixture was dispersed in 25ml of ethanol and 25ml of HCl solution (concentration 2mol / L) overnight, and then extracted with chloroform. The mixture was washed with 5% NaHCO3 until neutral, and then dehydrated with anhydrous calcium carbonate and purified by column chromatography to obtain the target product, i.e., CIAA.

[0055] The prepared CIAA is chemically bonded by an assembler containing a hydrophilic functional group and a non-polar restricting assembler, and CIAA is non-polar; among them, the assembler is S-4 in Table 1; the non-polar restricting assembler is Q-3 in Table 2; CIAA can form nanospheres through self-assembly in the aqueous phase.

[0056] Example 4

[0057] A preparation method of CIAA, the specific process is as follows:

[0058] 0.12gC8H 17 -NH2, 0.024g naphthalenetetracarboxylic anhydride, 1g imidazole and 4ml o-dichlorobenzene were placed in a round-bottom flask, condensed and refluxed, heated in an oil bath at 140°C under argon atmosphere, stirred for 6h, and after cooling, dispersed in 25ml ethanol and 25ml 2mol / L HCl solution overnight; after extraction with chloroform, the mixture was washed with 5% NaHCO3 until neutral, dehydrated with anhydrous calcium carbonate, and purified by column chromatography to obtain the target product, i.e., CIAA.

[0059] The prepared CIAA is composed of one assembler containing a hydrophilic functional group and two non-polar restricting assemblers chemically bonded together, and CIAA is non-polar; among them, the assembler is S-1 in Table 1; the non-polar restricting assembler is Q-4 in Table 2; CIAA can form nanospheres through self-assembly in the aqueous phase.

[0060] Example 5

[0061] A preparation method of CIAA, comprising the following steps:

[0062] (1) 2 g of perylene tetracarboxylic anhydride and 29.4 mL of concentrated sulfuric acid were added to a 100 mL three-necked flask in sequence, and stirred at 55 ° C for 24 h. Then, 0.05 g of iodine was added to the mixture, and stirring was continued for 5 h. Subsequently, 0.58 mL of liquid bromine was added dropwise at a controlled rate of 1 h. The temperature was raised to 85 ° C and stirring was continued for 24 h. The excess bromine was removed with N2 atmosphere, 30 mL of ice water was added, and the mixture was cooled, filtered, and washed with 18.00 mL of 86% H2SO4 by mass, and then washed with double ice water to obtain a crude product (2.70 g, 96%). The crude product was recorded as PTCDA-Br without separation and purification and was directly used in the next synthesis.

[0063] (2) After adding 0.50 g of the crude PTCDA-Br obtained above and 15 mL of 1-methyl-2-pyrrolidone into a 100 mL three-necked flask, the mixture was stirred at 25°C for 1 h; then 0.587 g of 2-ethylhexylamine was added, followed by 16.8 g of glacial acetic acid, the temperature was raised to 85°C, and the reaction was continued under N2 protection for 7 h; cooled to room temperature, 120 mL of methanol was added, and the mixture was stirred overnight; finally, the mixture was filtered, dried in vacuo, and separated and purified by silica gel (300 mesh) column chromatography to obtain a red solid, which was recorded as 1,7-Br-PDI-EH.

[0064] (3) 100 mg of the isolated 1,7-Br-PDI-EH was added to a round-bottom flask and dissolved in 20 mL of tetrahydrofuran (THF). A magnetic stirrer was added and stirred for 1 h to allow the 1,7-Br-PDI-EH to fully dissolve. 60.8 mg of potassium carbonate and 108.48 mg of 18-crown-6-ether were then added, followed by 0.2 g of (n=12), stirred at room temperature for 2 h to stop the reaction; after rotary evaporation, water and chloroform were added for extraction to obtain a chloroform extract, and finally purified by column chromatography to obtain the target product, namely CIAA.

[0065] The prepared CIAA is composed of one assembler containing a hydrophilic functional group and two non-polar restricting assemblers chemically bonded together, and CIAA is non-polar; among them, the assembler is S-2 in Table 1; the non-polar restricting assembler is Q-5 in Table 2; CIAA can form nanospheres through self-assembly in the aqueous phase.

[0066] Example 6

[0067] A preparation method of CIAA, the specific process is as follows:

[0068] (1) 2 g of perylene tetracarboxylic anhydride and 29.40 mL of concentrated sulfuric acid were added to a 100 mL three-necked flask in sequence, and stirred at 55°C for 24 h. Then, 0.05 g of iodine was added to the mixture, and stirring was continued for 5 h. Subsequently, 0.29 mL of liquid bromine was added dropwise at a controlled rate of 1 h. The mixture was heated to 85°C and stirred for 24 h. Excess bromine was removed with N2 atmosphere, 30.00 mL of ice water was added, the mixture was cooled, filtered, and washed with 18.00 mL of 86% H2SO4, and then washed with double the amount of ice water to obtain a crude product. The crude product was not separated or purified and was recorded as PTCDA-Br and used directly in the next step of synthesis.

[0069] (2) 0.50 g of the crude PTCDA-Br product prepared above and 15.00 mL of 1-methyl-2-pyrrolidone were added to a 100 mL three-necked flask in sequence, and the mixture was stirred at 25°C for 1 h. Then, 0.84 g of dodecylamine was added, followed by 16.80 g of glacial acetic acid. The temperature was raised to 90°C and the reaction was continued under N2 protection for 7 h. The mixture was cooled to room temperature, 120.00 mL of methanol was added, and the mixture was stirred overnight. The mixture was filtered, dried in vacuo, and purified by silica gel (200 mesh) column chromatography (mobile phase: chloroform / n-hexane = 2:3) to obtain a red solid, which was recorded as 1-Br-PDI-C. 12 ;

[0070] (3) Add 100 mg of the separated 1-Br-PDI-C into the round-bottom flask. 12 , dissolve it in 20 mL of tetrahydrofuran, add a magnetic stirrer and stir for 1 h to make 1-Br-PDI-C12 After fully dissolving in the solution, 60.80 mg of potassium carbonate and 108.48 mg of 18-crown-6-ether were added, followed by a slightly excess of 0.1 g It can be observed that the solution immediately turns purple and is stirred at room temperature for 2 hours to stop the reaction; water and chloroform are then added for extraction after rotary evaporation to obtain a chloroform extract; and finally, the target product, i.e., CIAA, is separated by column chromatography.

[0071] The prepared CIAA is chemically bonded by an assembler containing a hydrophilic functional group and a non-polar restricting assembler, and CIAA is non-polar; wherein, the assembler is S-6 in Table 1; the non-polar restricting assembler is Q-1 in Table 2; CIAA can form nanospheres through self-assembly in the aqueous phase.

[0072] Example 7

[0073] A method for preparing an aqueous dispersion of nanoparticles based on non-polar molecules, comprising the following steps:

[0074] (1) The CIAA prepared in Example 1 was dissolved in tetrahydrofuran at a mass-to-volume ratio of 1 mg:1 mL to form a uniform CIAA / tetrahydrofuran solution. Ultrapure water (resistivity of 18 MΩ*cm) was then rapidly added (within 5 s) to the CIAA / tetrahydrofuran solution at a volume ratio of 1:10 to obtain a colloid with Tyndall effect.

[0075] (2) The colloid prepared in step (1) was transferred to a dialysis bag with a molecular weight cut-off greater than 500, and the colloid was dialyzed with pure water. The pure water for dialysis was then replaced 1.5 h, 4 h, and 8 h after the start of dialysis. The volume ratio of pure water to dispersion for each dialysis was 2000:11. The dialysis was completed after 24 h, and tetrahydrofuran in the colloid was removed to obtain an aqueous dispersion of nanoparticles based on non-polar molecules with a concentration of 0.1 mg / mL.

[0076] In the prepared aqueous dispersion of nanospheres based on non-polar molecules, the average particle size of the nanospheres is 50 nm, the polydispersity index is 0.1, and the Zeta potential is -60 mV. The particle size and polydispersity index of the nanospheres are measured by dynamic laser light scattering (DLS) test method. The test temperature is 25°C, the test time is 5 minutes, and the test temperature of the Zeta potential is 25°C.

[0077] Example 8

[0078] A method for preparing an aqueous dispersion of nanoparticles based on non-polar molecules, comprising the following steps:

[0079] (1) The CIAA prepared in Example 2 was dissolved in tetrahydrofuran at a mass-to-volume ratio of 2 mg:1 mL to form a uniform CIAA / tetrahydrofuran solution. Ultrapure water (resistivity of 18 MΩ*cm) was then rapidly added (within 6 s) to the CIAA / tetrahydrofuran solution at a volume ratio of 1:8 to obtain a colloid with Tyndall effect.

[0080] (2) The colloid prepared in step (1) was transferred to a dialysis bag with a molecular weight cut-off greater than 500, and the colloid was dialyzed with pure water. The pure water for dialysis was then replaced 1.5 h, 4 h, and 8 h after the start of dialysis. The volume ratio of pure water to dispersion for each dialysis was 2000:11. The dialysis was completed after 24 h, and tetrahydrofuran in the colloid was removed to obtain an aqueous dispersion of nanoparticles based on non-polar molecules with a concentration of 0.25 mg / mL.

[0081] In the prepared aqueous dispersion of nanospheres based on non-polar molecules, the average particle size of the nanospheres is 70 nm, the polydispersity index is 0.15, and the Zeta potential is -55 mV. The particle size and polydispersity index of the nanospheres are measured by dynamic laser light scattering (DLS) test method. The test temperature is 26°C, the test time is 5 minutes, and the Zeta potential test temperature is 26°C.

[0082] Example 9

[0083] A method for preparing an aqueous dispersion of nanoparticles based on non-polar molecules, comprising the following steps:

[0084] (1) The CIAA prepared in Example 3 was dissolved in tetrahydrofuran at a mass-to-volume ratio of 4 mg:1 mL to form a uniform CIAA / tetrahydrofuran solution. Ultrapure water (resistivity of 18 MΩ*cm) was then rapidly added (within 7 s) to the CIAA / tetrahydrofuran solution at a volume ratio of 1:7 to obtain a colloid with Tyndall effect.

[0085] (2) The colloid prepared in step (1) was transferred to a dialysis bag with a molecular weight cut-off greater than 500, and the colloid was dialyzed with pure water. The pure water for dialysis was then replaced 1.5 h, 4 h, and 8 h after the start of dialysis. The volume ratio of pure water to dispersion for each dialysis was 3000:11. The dialysis was completed after 24 h, and tetrahydrofuran in the colloid was removed to obtain an aqueous dispersion of nanoparticles based on non-polar molecules with a concentration of 0.57 mg / mL.

[0086] In the prepared aqueous dispersion of nanospheres based on non-polar molecules, the average particle size of the nanospheres is 100 nm, the polydispersity index is 0.3, and the Zeta potential is -53 mV. The particle size and polydispersity index of the nanospheres are measured by dynamic laser light scattering (DLS) test method. The test temperature is 27°C, the test time is 5 minutes, and the test temperature of the Zeta potential is 27°C.

[0087] Example 10

[0088] A method for preparing an aqueous dispersion of nanoparticles based on non-polar molecules, comprising the following steps:

[0089] (1) The CIAA prepared in Example 4 was dissolved in tetrahydrofuran at a mass-to-volume ratio of 6 mg:1 mL to form a uniform CIAA / tetrahydrofuran solution. Ultrapure water (resistivity of 18 MΩ*cm) was then rapidly added (within 8 s) to the CIAA / tetrahydrofuran solution at a volume ratio of 1:5 to obtain a colloid with Tyndall effect.

[0090] (2) The colloid prepared in step (1) was transferred to a dialysis bag with a molecular weight cut-off greater than 500, and the colloid was dialyzed with pure water. The pure water for dialysis was then replaced 1.5 h, 4 h, and 8 h after the start of dialysis. The volume ratio of pure water to dispersion for each dialysis was 3000:11. The dialysis was completed after 24 h, and tetrahydrofuran in the colloid was removed to obtain an aqueous dispersion of nanoparticles based on non-polar molecules with a concentration of 1.2 mg / mL.

[0091] In the prepared aqueous dispersion of nanospheres based on non-polar molecules, the average particle size of the nanospheres is 120 nm, the polydispersity index is 0.5, and the Zeta potential is -50 mV. The particle size and polydispersity index of the nanospheres are measured by dynamic laser light scattering (DLS) test method. The test temperature is 28°C, the test time is 4 minutes, and the test temperature of the Zeta potential is 28°C.

[0092] Example 11

[0093] A method for preparing an aqueous dispersion of nanoparticles based on non-polar molecules, comprising the following steps:

[0094] (1) The CIAA prepared in Example 5 was dissolved in tetrahydrofuran at a mass-to-volume ratio of 7 mg:1 mL to form a uniform CIAA / tetrahydrofuran solution. Ultrapure water (resistivity of 18 MΩ*cm) was then rapidly added (within 9 s) to the CIAA / tetrahydrofuran solution at a volume ratio of 1:5 to obtain a colloid with Tyndall effect.

[0095] (2) The colloid prepared in step (1) was transferred to a dialysis bag with a molecular weight cut-off greater than 500, and the colloid was dialyzed with pure water. The pure water for dialysis was then replaced 1.5 h, 4 h, and 8 h after the start of dialysis. The volume ratio of pure water to dispersion for each dialysis was 3000:11. The dialysis was completed after 24 h, and tetrahydrofuran in the colloid was removed to obtain an aqueous dispersion of nanoparticles based on non-polar molecules with a concentration of 1.4 mg / mL.

[0096] In the prepared aqueous dispersion of nanospheres based on non-polar molecules, the average particle size of the nanospheres is 150 nm, the polydispersity index is 0.6, and the Zeta potential is -47 mV. The particle size and polydispersity index of the nanospheres are measured by dynamic laser light scattering (DLS) test method. The test temperature is 29°C, the test time is 4 minutes, and the test temperature of the Zeta potential is 29°C.

[0097] Example 12

[0098] A method for preparing an aqueous dispersion of nanoparticles based on non-polar molecules, comprising the following steps:

[0099] (1) The CIAA prepared in Example 6 was dissolved in tetrahydrofuran at a mass-to-volume ratio of 10 mg:1 mL to form a uniform CIAA / tetrahydrofuran solution. Ultrapure water (resistivity of 18 MΩ*cm) was then rapidly added (within 9 s) to the CIAA / tetrahydrofuran solution at a volume ratio of 1:5 to obtain a colloid with Tyndall effect.

[0100] (2) The colloid prepared in step (1) was transferred to a dialysis bag with a molecular weight cut-off greater than 500, and the colloid was dialyzed with pure water. The pure water for dialysis was then replaced 1.5 h, 4 h, and 8 h after the start of dialysis. The volume ratio of pure water to dispersion for each dialysis was 4000:11. The dialysis was completed after 24 h, and tetrahydrofuran in the colloid was removed to obtain an aqueous dispersion of nanoparticles based on non-polar molecules with a concentration of 2 mg / mL.

[0101] In the prepared aqueous dispersion of nanospheres based on non-polar molecules, the average particle size of the nanospheres is 180 nm, the polydispersity index is 0.65, and the Zeta potential is -45 mV. The particle size and polydispersity index of the nanospheres are measured by dynamic laser light scattering (DLS) test method. The test temperature is 30°C, the test time is 3 minutes, and the test temperature of the Zeta potential is 30°C.

Claims

1. A nanosphere, characterized in that: It is formed by self-assembly of CIAA in water phase; CIAA is chemically bonded by one assembly subunit containing a hydrophilic functional group and one to two non-polar limiting assembly subunits, and CIAA is non-polar; The assembly subunit containing a hydrophilic functional group is Where * is the chemical bonding position; The non-polar constrained assembly subunit is a group having a nanometer-sized three-dimensional structure, or a group that can be condensed into a nanometer-sized three-dimensional structure due to hydrophobic interaction in the aqueous phase; The group having a nanometer-sized three-dimensional structure is Wherein, * represents a chemical bonding position, R represents an isobutyl group or an isooctyl group, and R1 and R2 are each independently selected from an alkyl chain having less than 20 carbon atoms.

2. The nanoparticles according to claim 1, characterized in that: The group that can shrink into a nanometer-sized three-dimensional structure due to hydrophobic interaction in the aqueous phase is an alkyl chain with more than 6 carbon atoms.

3. A method for preparing an aqueous dispersion of nanoparticles based on non-polar molecules, characterized by: First, CIAA is dissolved in tetrahydrofuran to form a CIAA / tetrahydrofuran solution, and then ultrapure water is added to the CIAA / tetrahydrofuran solution to obtain a colloid. Finally, the tetrahydrofuran in the colloid is removed by dialysis to obtain the aqueous dispersion of nanoparticles based on non-polar molecules. CIAA forms nanospheres by self-assembly in aqueous phase. CIAA is chemically bonded by one assembly subunit containing a hydrophilic functional group and one to two non-polar limiting assembly subunits, and CIAA is non-polar. The assembly subunit containing a hydrophilic functional group is Wherein * is a chemical bonding position; the non-polar constrained assembly subunit is a group having a nanometer-sized three-dimensional structure, or a group that can be condensed into a nanometer-sized three-dimensional structure due to hydrophobic interaction in the aqueous phase; The group having a nanometer-sized three-dimensional structure is Wherein, * is a chemical bonding position, R is an isobutyl group or an isooctyl group, and R1 and R2 are each independently selected from an alkyl chain having less than 20 carbon atoms; The mass volume ratio of CIAA to tetrahydrofuran is 1 mg:1 mL to 10 mg:1 mL, and the volume ratio of CIAA / tetrahydrofuran solution to ultrapure water is 1:5 to 1:10; The concentration of the nano-microsphere aqueous phase dispersion based on non-polar molecules is 0.1-2 mg / mL.

4. The method according to claim 3, characterized in that The dialysis method for removing tetrahydrofuran from the colloid is as follows: the colloid is transferred to a dialysis bag with a molecular weight cutoff > 500, and the colloid is dialyzed with pure water. The pure water for dialysis is replaced 1.5 hours, 4 hours, and 8 hours after the start of dialysis. The volume ratio of pure water to dispersion liquid for each dialysis is 2000-4000:

11. The dialysis is completed after 24 hours.

5. The method according to claim 3, characterized in that The particle size of the nano-microspheres in the aqueous phase dispersion based on non-polar molecules is 50-200 nm, the polydispersity index is 0.1-0.7, and the Zeta potential is -60--40 mV.

6. The method according to claim 3, characterized in that The group that can shrink into a nanometer-sized three-dimensional structure due to hydrophobic interaction in the aqueous phase is an alkyl chain with more than 6 carbon atoms.

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