A method for self-assembly of inorganic nanoparticles based on host-guest interaction

Abstract

The application discloses a controllable assembly method of nanoparticles. The method is realized by complexing carboxyl-modified pillar[5]arene (CP[5]A) and pyrene butyric acid grafted organic imidazole salt through host-guest interaction. Through a two-step simple substitution reaction, 1-methyl-3-(10-(4-pyrene-1-butanoic acid)-chrysene-1H-imidazole bromide and derivatives containing different carbon numbers are synthesized, which are mixed with the reported CP[5]A to obtain the assembly system. By adjusting the concentration of the host and guest organic matters and the chain length of the guest organic matter, AuNPs can be controllably assembled and form well-defined one-dimensional and two-dimensional structures, especially the fine assembly of AuNPs can be realized. The assembly system has high stability and can exist stably for months. Meanwhile, the assembly system has good universality and can be used to assemble different types of nanoparticles, such as silver nanoparticles, silver nanosheets, iron gold nanoparticles and gold nanorods, and is a simple and universal assembly platform.

Description

Technical Field

[0001] This invention relates to the field of functional modification of nanoparticles, and specifically to a method for the self-assembly of inorganic nanoparticles based on host-guest interactions. Background Technology

[0002] Metal nanoparticles are considered an important class of materials in the development of nanoscience and nanotechnology. Surface functionalization of metal nanoparticles plays a crucial role in optical properties, catalytic performance, and assembly activity. Over the past few decades, extensive research has been conducted on a wide variety of nanoparticles, such as gold nanoparticles (AuNPs), silver nanoparticles (AgNPs), Fe3O4 nanoparticles (Fe3O4NPs), quantum dots (QDs), CuS nanoparticles, and upconversion nanoparticles (UCNPs). Metal nanoparticles exhibit interesting optical, electronic, and magnetic properties depending on their size, shape, and composition. Through precise control, inorganic nanoparticles can be organized into discrete clusters, allowing for fine-tuning of their collective properties derived from the interactions of surface plasmon polaritons, excitons, and magnetic moments. Inorganic nanoparticle clusters have broad applications in sensing, catalysis, biomedicine, and surface-enhanced Raman scattering (SERS) spectroscopy.

[0003] The design and synthesis of novel macrocyclic compounds have propelled the rapid development of supramolecular chemistry and materials science. With the advancements in macrocyclic chemistry, including crown ethers, cyclodextrins, calixarenes, and cucurbiturates, columnar [n]arenes (n = 5-15), first reported by Ogoshi et al. in 2008, have become a rising star in macrocyclic chemistry. Columnar [n]arenes are composed of n hydroquinone units linked at the 2 and 5 positions via methylene bridges, possessing a rigid columnar molecular structure and hydrophobic cavities rich in π electrons, which facilitates the binding of electron-deficient guests. Due to the high modifiability of columnar [n]arenes, many derivatives with different functional groups can be obtained through catalytic 1,4-dimethoxybenzene cyclization or post-synthetic modification. The multifunctional modification of columnar [n]arenes and their unique host-guest properties have expanded their applications in organic and aqueous phases. Among the studied metal nanoparticles, gold nanoparticles have attracted considerable attention due to their inherent localized surface plasmon resonance (LSPR) effect and surface-enhanced Raman scattering (SERS) capability. The combination of AuNPs and supramolecular macrocycles will effectively combine and enhance the properties of both, such as the electrical, thermal, and catalytic properties of gold nanoparticles and the molecular recognition ability of the macrocycle host, expanding their potential applications in fields such as nanosensors, drug delivery carriers, and cyclic extractants.

[0004] AuNPs have been successfully stabilized by water-soluble or amphiphilic columnar [5] aromatics functionalized with imidazole, amino, carboxylic acid and amino groups, exhibiting good chemical stability and catalytic and sensing potential. Li et al. designed and synthesized a novel water-soluble macrocyclic columnar aromatic (CP[5]A) that can be used to prepare gold nanoparticles (AuNPs) in situ. At the same time, CP[5]A-modified AuNPs can achieve supramolecular self-assembly under the action of suitable guest molecules. This novel hybrid material can be used for sensing and detection of the herbicide paraquat. However, much research is still focused on the synthesis of columnar [5] aromatics and their derivatives, their host-guest interactions and their supramolecular self-assembly. The combination of columnar [5] aromatics with AuNPs and the resulting controlled assembly or even fine assembly of AuNPs have not been explored to a large extent. Summary of the Invention

[0005] The purpose of this invention is to address the shortcomings of existing supramolecular organic materials, such as the inability to precisely and controllably assemble nanoparticles and the poor stability of assembled nanoparticle aggregates. By designing the interaction between the host and guest components in the synthesis, this invention provides a simple and universal method for assembling nanoparticles.

[0006] Another object of the present invention is to provide a method for achieving the fine assembly of nanoparticles.

[0007] The preparation method of the main carboxyl-modified columnar aromatic hydrocarbon (CP[5]A) includes the following steps:

[0008]

[0009] S11, Preparation of dimethoxy[5] aromatics (b): Using boron trifluoride ether as a catalyst, 1,4-dimethoxybenzene (compound a) and paraformaldehyde were mixed in a certain proportion, and dichloromethane was used as a solvent. After stirring at room temperature for a certain time, a small amount of water was added for quenching. The resulting mixture was washed with water, the organic phase was collected, concentrated, and then subjected to column chromatography to obtain dimethoxy[5] aromatics (compound b).

[0010] S12, Preparation of compound c: Disperse compound b in dichloromethane solvent, add a certain amount of boron tribromide to the mixed solution under ice bath conditions and stir for a certain time, pour the reaction solution into cold water and add dilute hydrochloric acid, filter and collect the solid to obtain compound c.

[0011] S13, Preparation of compound d: Compound c was dispersed in acetonitrile solution, a certain amount of potassium carbonate was added, the mixture was stirred at room temperature for a period of time, a small amount of KI and excess ethyl bromoacetate were added to the solution and then heated under reflux for a period of time. After the reaction was completed and cooled to room temperature, the mixture was filtered and washed with chloroform. The filtrate was concentrated, and the mixture was separated by column chromatography. The crude product was crystallized by slow diffusion of n-hexane in chloroform solution. After filtration and drying, ethoxycarbonyl-substituted P[5]A(d) was obtained.

[0012] S14, Preparation of compound e: Compound d was dispersed in a tetrahydrofuran solution and a certain amount of sodium hydroxide aqueous solution was added. The mixed solution was heated under reflux for a period of time, cooled to room temperature, and concentrated under reduced pressure. The residue was diluted in a certain amount of water and then acidified with hydrochloric acid. The resulting precipitate was collected by filtration, washed with water, and dried under vacuum to obtain CP[5]A(e).

[0013] S15, Preparation of compound f: Disperse compound e in deionized water, and then add sodium hydroxide solution dropwise to the mixture until the reaction mixture becomes transparent. The final product (f) of Cp[5]A is obtained by vacuum drying.

[0014] In step S11, the concentration of the boron trifluoride diethyl ether catalyst was 64 wt% and the volume was 5.92 mL; the purity of the solvent dichloromethane was 99.5% and the volume was 30 mL; the mixing ratio of 1,4-dimethoxybenzene (compound a) to paraformaldehyde was 1:3; the stirring time was 10 min; the concentration temperature was 60 °C; the chromatography solvent used was a 1:1 mixture of dichloromethane and petroleum ether; and the yield of the dimethoxy column[5] aromatic hydrocarbons obtained was 56%. 1 H NMR (300MHz, CDCl3, 25℃) δ (ppm): 6.76 (s, 10H), 3.77 (s, 10H), 3.65 (s, 30H).

[0015] In step S12, the amount of compound b is 3 mmol and the mass is 2.2 g; the purity of the solvent dichloromethane is 99.5% and the volume is 50 ml; the mixing ratio of compound b to boron tribromide is 1:50, the amount of boron tribromide is 150 mmol and the mass is 37.85 g; the stirring time is 24 h, the concentration of dilute hydrochloric acid is 37 wt%; and the yield of compound c obtained is 85%. 1 H NMR (300MHz, CD3COCD3, 25°C); δ (ppm): 6.66 (s, 10H), 3.59 (s, 10H), 7.97 (s, 10H).

[0016] In step S13, the amount of compound c is 2.55 mmol and the mass is 1.56 g; the concentration of the solvent acetonitrile is 99.5% and the volume is 60 ml; the amount of potassium carbonate is 25.5 mmol and the mass is 3.52 g; the mixture is stirred at room temperature for 30 min; the mass of KI added is 20 mg; the mixing ratio of compound c to ethyl bromoacetate is 1:22; the amount of compound c is 56.1 mmol and the mass is 9.37 g; the reaction heating temperature is 100 °C and the stirring time is 18 h; the yield of compound d obtained is 80%. 1 H NMR (300MHz, CDCl3, 25℃) δ (ppm): 7.05 (s, 10H), 4.54 (q, J = 15Hz, 20H), 4.09 (m, J = 6Hz, 20H), 3.86 (s, 10H), 0.98 (t, J = 6Hz, 30H).

[0017] In step S14, the amount of compound d is 1.0 mmol and the mass is 1.47 g; the concentration of the solvent tetrahydrofuran is 99.5% and the volume is 60 ml; the reaction heating temperature is 100 °C and the stirring time is 15 h; the concentration of hydrochloric acid is 37 wt% and the volume of water used is 100 ml; the yield of compound e obtained is 92%. 1 H NMR (300MHz, CD3SOCD3, 25℃) δ (ppm): 12.93 (s, 10H), 7.11 (s, 10H), 4.69 (d, J = 15Hz, 10H), 4.41 (d, J = 15Hz, 10H), 3.74 (s, 10H).

[0018] In step S15, the mass of compound e is 0.24 g, the volume of deionized water is 3 ml, and the sodium hydroxide solution is prepared by dissolving 80 mg of sodium hydroxide in 1 ml of deionized water. The yield of compound f is 95%. 1 13C NMR (500MHz, D2O, 25C) δ (ppm): 177.496, 149.239, 128.593, 114.588, 67.722, 29.086.

[0019] The preparation method of the guest 1-methyl-3-(10-(4-pyrene-1-butyric acid)-decyl-1H-imidazolium bromide and derivatives containing different carbon numbers includes the following steps (taking n=10 as an example):

[0020]

[0021] S21, Preparation of Compound 1: 1-Pyrenebutyric acid was dispersed in acetonitrile solution, potassium carbonate was added, and excess 1,10-dibromodecane was added. The mixture was heated under reflux for a period of time, cooled to room temperature, filtered, and the filtrate was washed with water and concentrated. The resulting mixture was separated by column chromatography to obtain Compound 1.

[0022] S22, Preparation of Compound 2: Compound 1 and methylimidazole are dispersed in an ethanol solution and heated under reflux for a period of time. After the reaction is complete, the solvent is removed by rotary evaporation, and the remaining mixture is subjected to steam distillation to remove the remaining methylimidazole, thus obtaining Compound 2.

[0023] In step S21, the amount of 1-pyrenebutyric acid is 10 mmol, and the mass is 2.88 g; the concentration of the solvent acetonitrile is 99.5%, and the volume is 150 ml; the mixing ratio of 1-pyrenebutyric acid and potassium carbonate is 1:1.5; the amount of potassium carbonate is 15 mmol, and the mass is 2.07 g; the mixing ratio of 1-pyrenebutyric acid and 1,10-dibromodecane is 1:5; the amount of 1,10-dibromodecane is 50 mmol, and the mass is 15 g; the reaction heating temperature is 110 °C, and the reaction time is 24 h; the chromatography solvent used is a 1:1 mixture of dichloromethane and petroleum ether; the yield of compound 1 obtained is 79%.

[0024] In step S22, the amount of compound 1 was 8 mmol and the mass was 4 g; the purity of the solvent ethanol was 99.5%; the mixing ratio of compound 1 and methylimidazole was 1:1.2; the amount of methylimidazole was 9.6 mmol and the mass was 0.78 g; the reaction was heated to 100°C. The yield of compound 2 was 82%.

[0025] The host and guest organic materials can be applied in the assembly of nanoparticles. The application method is as follows:

[0026] Dissolve 0.119 g of CP[5]A in 10 mL of deionized water, sonicate, take 1 mL, and add 9 mL of deionized water. This will give you a 1 mM CP[5]A aqueous solution. The preparation methods for the guest 1-methyl-3-(10-(4-pyrene-1-butyric acid)-decyl-1H-imidazolium bromide and derivative solutions containing different carbon numbers are as described above. Different volumes of the prepared CP[5]A aqueous solution and different volumes of the guest solution were mixed in a 1:1 ratio. Then, 500 μL of 13 nm AuNPs was added to the mixed solution, and then an appropriate amount of deionized water was added to dilute it to 1 mL. The color of the solution was photographed with a digital camera to make a standard colorimetric card; at the same time, the ultraviolet-visible spectrum of the above mixed solution was scanned with a spectrophotometer. It can be found through the ultraviolet spectral curve that the characteristic peak of AuNPs has red-shifted. The assembly of AuNPs was confirmed by transmission electron microscopy. The degree of assembly is positively correlated with the concentration of the host and guest organic compounds and the chain length of the guest organic compounds.

[0027] This invention provides a novel method for assembling nanoparticles. Based on the previously reported CP[5]A, guest 1-methyl-3-(10-(4-pyrene-1-butyric acid)-decyl-1H-imidazolium bromide and derivatives containing different carbon numbers were designed and synthesized. Through the interaction between the host and guest, as well as π-π stacking and electrostatic interaction, the controllable assembly of nanoparticles was achieved, especially the fine assembly of nanoparticles. This assembly method has good stability and can remain stable for several months at room temperature. At the same time, this method also has good universality and can be used to assemble different kinds of nanoparticles. Attached Figure Description

[0028] Figure 1 This is a schematic diagram illustrating the principle of the self-assembly of inorganic nanoparticles based on host-guest interaction in this invention.

[0029] Figure 2 The 1H NMR spectrum of the guest 1-methyl-3-(10-(4-pyrene-1-butyric acid)-decyl-1H-imidazolium bromide.

[0030] Figure 3 These are the UV-Vis scanning spectra and transmission electron microscopy images of Au nanoparticles before and after assembly in this invention. Figure 3 In the image, (a) is a transmission electron microscope (TEM) image of nanoparticles assembled using 1 μL of host-guest mixture; (b) is a TEM image of nanoparticles assembled using 5 μL of host-guest mixture; (c) is a TEM image of nanoparticles assembled using 10 μL of host-guest mixture; and (d) is a TEM image of nanoparticles assembled using 20 μL of host-guest mixture.

[0031] Figure 4 These are transmission electron microscope (TEM) images of guests assembled using different chain lengths in this invention. Figure 4 In the image, (a) is a scanning electron microscope (SEM) image of an assembly using a guest with 4 C chain lengths; (b) is a SEM image of an assembly using a guest with 6 C chain lengths; (c) is a SEM image of an assembly using a guest with 8 C chain lengths; and (d) is a SEM image of an assembly using a guest with 10 C chain lengths.

[0032] Figure 5 To investigate the universality of the self-assembly method of inorganic nanoparticles based on host-guest interaction of this invention. Figure 5 In the image, (a) is a scanning transmission electron microscope (STEM) image of discrete gold nanorods; (b) is a STEM image of gold nanorod clusters assembled using this method; (c) is a STEM image of discrete Fe3O4@Au nanoparticles; and (d) is a STEM image of Fe3O4@Au nanoparticle clusters assembled using this method.

[0033] Figure 6 To investigate the stability of the inorganic nanoparticle self-assembly method based on host-guest interaction of this invention. Figure 6 In the table, (a) is a freshly prepared solution of Au nanoparticles and a solution of assembled gold nanoparticle clusters; (b) is a solution of (a) after being left at room temperature for one month; (c) is a solution of (a) after being left at room temperature for two months; and (d) is a solution of (a) after being left at room temperature for three months. Detailed Implementation

[0034] The following embodiments will further illustrate the present invention with reference to the accompanying drawings.

[0035] Figure 1 A schematic diagram illustrating the principle of the self-assembly of inorganic nanoparticles based on host-guest interactions described in this invention is provided. First, a solution of the host macrocycle is mixed with a guest organic solution of equal concentration to form a 1:1 complex. Then, 500 μL of Au nanoparticles are added to the mixed solution. Since the host macrocycle contains oxygen at its terminal, it can form strong coordination bonds with AuNPs, thereby adsorbing onto the surface of the AuNPs. Furthermore, each guest organic compound contains a pyrene molecule, which can introduce π-π stacking interactions in aqueous solution, thus self-assembling into a highly ordered pyrene-based molecular layer. Simultaneously, the compound also has positively charged imidazole groups grafted at its terminal, which can bind to AuNPs through electrostatic interactions. By controlling the concentration of the host and guest organic compounds and the chain length of the guest organic compounds, the degree of nanoparticle assembly can be controlled.

[0036] Figure 2 The 1H NMR spectrum of the guest 1-methyl-3-(10-(4-pyrene-1-butyric acid)-decyl-1H-imidazolium bromide is given. 1H NMR(400MHz,Chloroform-d)δ10.35(s,1H),8.28(d,J=9.2Hz,1H),8.14(dd,J=7.6,3.8H z,2H),8.09(d,J=8.5Hz,2H),8.04–7.93(m,3H),7.84(d,J=7.8Hz,1H),7.12(d,2H),4.17 (t,J=7.5Hz,2H),4.06(t,J=6.6Hz,2H),4.03(s,3H),3.36(t,2H),2.44(t,J=7.2Hz,4H) ,2.16(p,J=7.3Hz,2H),1.79(p,J=7.2Hz,2H),1.59(p,J=6.8Hz,2H),1.33–1.21(m,10H).

[0037] Figure 3 The UV-Vis scanning spectra and transmission electron microscopy (TEM) images of the Au nanoparticles before and after assembly according to this invention are presented. Under different host-guest concentrations, adding 500 μL of AuNPs to form AuNPs aggregates yielded different self-assembled structures, and the corresponding UV-Vis spectra are shown below. Figure 3 As shown on the left, with increasing host and guest concentrations, the SPR peak intensity of AuNPs at 520 nm gradually increases and undergoes a red shift, accompanied by a corresponding change in solution color. The observed changes in absorption spectrum and solution color further demonstrate that AuNPs undergo self-assembly in solution. Figure 3 (a) to (d) are transmission electron microscopy images of nanoparticles assembled using 1 μL, 5 μL, 10 μL, and 20 μL of host and guest materials, respectively. As the host and guest concentrations increase, the assembly degree of AuNPs also changes, and the aggregates gradually change from a one-dimensional chain-like self-assembled structure to a 2D network structure.

[0038] Figure 4 Transmission electron microscope (TEM) images of the assembled objects with different chain lengths as described in this invention are presented. Figure 4 (a)–(d) are electron micrographs of the assembly of guest organic compounds with 4, 6, 8, and 10 carbon atoms, respectively. Equal concentrations of guest organic compounds were mixed with host macrocycles, and AuNPs were added. As shown in the figure, the longer the guest organic compound chain, the greater the degree of AuNP assembly, resulting in more aggregated clusters; conversely, the shorter the organic ligand chain, the weaker the degree of assembly, and the more dispersed the resulting clusters.

[0039] The performance of this method will be examined in detail below with reference to specific embodiments.

[0040] Example 1:

[0041] To verify the universality of the method of this invention, it was applied to Au nanorods and Fe3O4@Au nanomaterials. Figure 5 As shown in the figure, the experimental results demonstrate that this method can achieve the controllable assembly of Au nanorods and Fe3O4@Au nanomaterials. This indicates that the method has good universality for nanomaterial assembly.

[0042] Example 2:

[0043] To verify the stability of the method of this invention, the states of freshly prepared Au nanoparticle solutions and Au nanoparticle aggregates assembled using different concentrations of host and guest agents were photographed and recorded, and photographed again after being placed at room temperature for one month, two months, and three months. Figure 6 As shown in the figure, the comparison revealed that both the Au nanoparticle solution and the assembled Au nanoparticle aggregates remained stable after several months at room temperature. This indicates that the proposed method exhibits good stability for nanomaterial assembly.

Claims

1. A method for the self-assembly of inorganic nanoparticles based on host-guest interactions, characterized in that... The specific method is as follows: Dissolve 0.119 g of carboxyl-modified column[5] aromatic hydrocarbon in 10 mL of deionized water, sonicate, take 1 mL, and add 9 mL of deionized water to obtain 1 mM CP[5]A aqueous solution; the preparation methods of the guest 1-methyl-3-(10-(4-pyrene-1-butyric acid)-decyl-1H-imidazolium bromide and derivative solutions containing different carbon numbers are as above. Take different volumes of the prepared carboxyl-modified column[5] aromatic hydrocarbon aqueous solution and different volumes of the guest solution and mix them in a 1:1 ratio. Then add 500 μL of 13 nm AuNPs to the mixed solution and add an appropriate amount of deionized water to dilute to 1 mL. The preparation method of the carboxyl-modified columnar aromatic hydrocarbon [5] includes: S11, Preparation of dimethoxy column[5] aromatics: using boron trifluoride ether as a catalyst, 1,4-dimethoxybenzene and paraformaldehyde are mixed in a certain proportion, and dichloromethane is used as a solvent. After stirring at room temperature for a certain time, a small amount of water is added to quench the mixture. The resulting mixture is washed with water, the organic phase is collected, concentrated, and column chromatography is performed to obtain dimethoxy column[5] aromatics. S12, Preparation of column[5] cyclic hydrocarbon: Disperse dimethoxy column[5] aromatic hydrocarbon in dichloromethane solvent, add a certain amount of boron tribromide to the mixed solution under ice bath conditions and stir for a certain time, pour the reaction solution into cold water and add dilute hydrochloric acid, filter and collect the solid to obtain compound column[5] aromatic hydrocarbon; S13, Preparation of ethoxycarbonyl-substituted column[5]arene: The compound column[5]arene was dispersed in an acetonitrile solution, a certain amount of potassium carbonate was added, the mixture was stirred at room temperature for a period of time, a small amount of KI and excess ethyl bromoacetate were added to the solution and then heated under reflux for a period of time; after the reaction was completed and cooled to room temperature, it was filtered and washed with chloroform, the filtrate was concentrated, the mixture was separated by column chromatography, and the crude product was crystallized by slow diffusion of n-hexane in chloroform solution. After filtration and drying, the ethoxycarbonyl-substituted column[5]arene was obtained. S14, Preparation of carboxylic acid-substituted columnar [5] aromatics: Ethoxycarbonyl-substituted columnar [5] aromatics are dispersed in tetrahydrofuran solution, and a certain amount of sodium hydroxide aqueous solution is added to it. The mixed solution is heated under reflux for a period of time, cooled to room temperature, and concentrated under reduced pressure. The residue is diluted in a certain amount of water and then acidified with hydrochloric acid. The precipitate is collected by filtration, washed with water, and dried under vacuum to obtain carboxylic acid-substituted columnar [5] aromatics. S15, Preparation of carboxyl-substituted columnar[5]arene: Carboxylic acid-substituted columnar[5]arene is dispersed in deionized water, and then sodium hydroxide solution is added dropwise to the mixture until the reaction mixture becomes transparent. The final product, carboxyl-substituted columnar[5]arene, is obtained by vacuum drying. The main carboxyl-substituted columnar aromatic hydrocarbon [5] used is assembled with the guest 1-methyl-3-(10-(4-pyrene-1-butyric acid)-decyl-1H-imidazolium bromide and derivatives containing different carbon numbers. The preparation steps of the guest 1-methyl-3-(10-(4-pyrene-1-butyric acid)-decyl-1H-imidazolium bromide and derivatives containing different carbon numbers include the following processes: S21, Preparation of 10-bromodecyl 4-(pyrene-1-yl)butyrate: 1-pyrenebutyric acid was dispersed in acetonitrile solution, potassium carbonate was added, and excess 1,10-dibromodecane was added; the mixture was heated under reflux for a period of time, cooled to room temperature, filtered, the filtrate was washed with water and concentrated, and the resulting mixture was separated by column chromatography to obtain compound 10-bromodecyl 4-(pyrene-1-yl)butyrate; S22, Preparation of 1-methyl-3-(10-(4-pyrene-1-butyric acid)-decyl-1H-imidazolium bromide: 10-bromodecyl 4-(pyrene-1-yl)butyric acid and methylimidazolium are dispersed in an ethanol solution and heated under reflux for a period of time. After the reaction is completed, the solvent is removed by rotary evaporation, and the remaining mixture is subjected to steam distillation to remove the remaining methylimidazolium, thereby obtaining 1-methyl-3-(10-(4-pyrene-1-butyric acid)-decyl-1H-imidazolium bromide.

2. The method for self-assembly of inorganic nanoparticles based on host-guest interaction as described in claim 1, characterized in that... In step S11, the concentration of the boron trifluoride diethyl ether catalyst was 64 wt% and the volume was 5.92 mL; the purity of the solvent dichloromethane was 99.5% and the volume was 30 mL; the mixing ratio of 1,4-dimethoxybenzene and paraformaldehyde was 1:3; the stirring time was 10 min; the concentration temperature was 60 °C; the chromatography solvent used was a 1:1 mixture of dichloromethane and petroleum ether; the yield of the dimethoxy column[5] aromatic hydrocarbon was 56%, and the 1H NMR (300 MHz, CDCl3, 25 °C) δ (ppm): 6.76 (s, 10H), 3.77 (s, 10H), 3.65 (s, 30H).

3. The method for self-assembly of inorganic nanoparticles based on host-guest interaction as described in claim 1, characterized in that... The amount of dimethoxy[5]arene in step S12 was 3 mmol and the mass was 2.2 g; the purity of the solvent dichloromethane was 99.5% and the volume was 50 ml; the mixing ratio of compound dimethoxy[5]arene to boron tribromide was 1:50, the amount of boron tribromide was 150 mmol and the mass was 37.85 g; the stirring time was 24 h and the concentration of dilute hydrochloric acid was 37 wt%; the yield of compound[5]arene was 85%, 1H NMR (300 MHz, CD3COCD3, 25 °C); δ (ppm): 6.66 (s, 10H), 3.59 (s, 10H), 7.97 (s, 10H).

4. The method for self-assembly of inorganic nanoparticles based on host-guest interaction as described in claim 1, characterized in that... In step S13, the amount of column[5]arene was 2.55 mmol and the mass was 1.56 g; the concentration of solvent acetonitrile was 99.5% and the volume was 60 ml; the amount of potassium carbonate was 25.5 mmol and the mass was 3.52 g; the mixture was stirred at room temperature for 30 min; the mass of KI added was 20 mg; the mixing ratio of compound column[5]arene to ethyl bromoacetate was 1:22; the amount of column[5]arene was 56.1 mmol and the mass was 9.37 g; the reaction heating temperature was 100 °C and the stirring time was 18 h; the yield of the obtained compound ethoxycarbonyl-substituted column[5]arene was 80%, 1H NMR (300MHz, CDCl3, 25°C) δ (ppm): 7.05 (s, 10H), 4.54 (q, J = 15Hz, 20H), 4.09 (m, J = 6Hz, 20H), 3.86 (s, 10H), 0.98 (t, J = 6Hz, 30H).

5. The method for self-assembly of inorganic nanoparticles based on host-guest interaction as described in claim 1, characterized in that... The amount of ethoxycarbonyl-substituted columnar [5]arene in step S14 was 1.0 mmol and the mass was 1.47 g; the concentration of the solvent tetrahydrofuran was 99.5% and the volume was 60 ml; the reaction heating temperature was 100 °C and the stirring time was 15 h; the concentration of hydrochloric acid was 37 wt% and the volume of water used was 100 ml; the yield of the obtained compound carboxylic acid-substituted columnar [5]arene was 92%, 1H NMR (300 MHz, CD3SOCD3, 25 °C) δ (ppm): 12.93 (s, 10H), 7.11 (s, 10H), 4.69 (d, J = 15 Hz, 10H), 4.41 (d, J = 15 Hz, 10H), 3.74 (s, 10H).

6. The method for self-assembly of inorganic nanoparticles based on host-guest interaction as described in claim 1, characterized in that... The mass of the carboxylic acid-substituted columnar [5]arene in step S15 was 0.24 g, the volume of deionized water was 3 ml, and the sodium hydroxide solution was prepared by dissolving 80 mg of sodium hydroxide in 1 ml of deionized water; the yield of the obtained compound, the carboxylic acid-substituted columnar [5]arene, was 95%. 1H NMR (500 MHz, D2O, 25 °C) δ (ppm): 6.80 (s, 10H), 4.51 (d, J = 20 Hz, 10H), 4.29 (d, J = 15 Hz, 10H), 3.86 (s, 10H); 13C NMR (500 MHz, D2O, 25 °C) δ (ppm): 177.496, 149.239, 128.593, 114.588, 67.722, 29.

086.

7. The method for self-assembly of inorganic nanoparticles based on host-guest interaction as described in claim 1, characterized in that... In step S21, the amount of 1-pyrenebutyric acid was 10 mmol, with a mass of 2.88 g; the concentration of the solvent acetonitrile was 99.5%, and the volume was 150 ml; the mixing ratio of 1-pyrenebutyric acid and potassium carbonate was 1:1.5; the amount of potassium carbonate was 15 mmol, with a mass of 2.07 g; the mixing ratio of 1-pyrenebutyric acid and 1,10-dibromodecane was 1:5; the amount of 1,10-dibromodecane was 50 mmol, with a mass of 15 g; the reaction heating temperature was 110 °C, and the reaction time was 24 h; the chromatography solvent used was a 1:1 mixture of dichloromethane and petroleum ether; the yield of the compound 4-(pyrene-1-yl)butyric acid 10-bromodecyl ester was 79%.

8. The method for self-assembly of inorganic nanoparticles based on host-guest interaction as described in claim 1, characterized in that... In step S22, the amount of 10-bromodecyl 4-(pyrene-1-yl)butyrate was 8 mmol, and the mass was 4 g; the purity of the solvent ethanol was 99.5%; the mixing ratio of 10-bromodecyl 4-(pyrene-1-yl)butyrate to methylimidazole was 1:1.2; the amount of methylimidazole was 9.6 mmol, and the mass was 0.78 g; the reaction was heated at 100 °C; and the yield of 1-methyl-3-(10-(4-pyrene-1-butyrate)-decyl-1H-imidazolium bromide was 82%.

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