Double-macrocyclic molecule based on column [5] arene and preparation and application of supramolecular system of double-macrocyclic molecule

Abstract

The invention provides preparation and application of a double-macrocyclic molecule based on pillar [5] arene and a supramolecular system of the double-macrocyclic molecule. A double-macrocyclic host molecule DNPB based on pillar [5] arene is synthesized firstly, the double-macrocyclic host molecule DNPB comprises two macrocyclic cavities with different rigidity and electronic structures, the cavities can be assembled with different objects step by step according to respective structural characteristics, and a supramolecular functional system HG1G2 with richer performance is constructed. Due to steric hindrance and packaging effect provided by double-large-ring assembly, the free radical emission characteristic of HG1G2 is remarkably improved. Meanwhile, by utilizing the good photoluminescence and photochromic properties of the supramolecular assembly system HG1G2, the supramolecular assembly system HG1G2 is introduced into polymethyl methacrylate, so that the photochromic and photoluminescence processes are more stable in a solid system, and the supramolecular assembly system HG1G2 is applied to hierarchical information encryption. Besides, different metal ions are introduced into a host-guest assembly system by utilizing cavities of different dimensions of the column [5] arene double-macrocyclic DNPB through an orthogonal self-assembly method of host-guest interaction and metal coordination interaction to construct a series of in-situ limited supramolecular polymer-based fluorescent nanoparticles (FSNPs), and the in-situ limited supramolecular polymer-based fluorescent nanoparticles are applied to cell imaging.

Description

Technical Field

[0001] The present invention relates to a bimacrocyclic molecule based on pillar[5]arene and a synthesis method thereof, and also relates to a supramolecular host-guest assembly system and supramolecular fluorescent nanoparticles constructed based on the bimacrocyclic molecule based on pillar[5]arene, and also relates to the application of the supramolecular host-guest assembly system as a photoluminescent and photochromic material in information encryption materials, and the application of supramolecular fluorescent nanoparticles in cell imaging. Background Art

[0002] The development of supramolecular functional materials based on macrocyclic assembly is a novel, interesting and promising direction. The construction of supramolecular functional materials using macrocyclic assembly can achieve functions that are difficult to achieve with single molecules. For example, the macrocyclic cavity can be used to enclose matching guests to achieve assembly, stimulus response, controlled release and other properties, which are widely used in the construction of advanced smart materials. On this basis, researchers have developed a series of advanced functional materials based on macrocyclic hosts, which show good application performance in the fields of host-guest recognition, separation, drug controlled release, catalysis, etc. However, the traditional assembly process is limited by the single cavity of the macrocycle, and its host-guest assembly mode also has certain limitations. Therefore, how to improve the assembly ability of macrocyclic compounds and develop supramolecular systems with specific functions has always been a huge challenge. Double macrocycles can provide cavities of different sizes and electronic structures, and can be assembled with different guests, so that they have richer host-guest properties.

[0003] As an important functional material, optical materials have been widely used in various fields of production and life. Among them, organic luminescent free radicals have become one of the hot topics of research due to their special molecular structure and have great application potential in the field of luminescence. Organic free radicals generally cannot exist stably due to their open-shell structure, making the stabilization of organic luminescent free radicals a very challenging study. Therefore, it is an interesting and challenging task to achieve stable and efficient free radical emission using supramolecular interactions. In addition, nanomaterials have broad application prospects in the biomedical field due to their unique physical and chemical properties. Nanoprobes with biocompatibility and strong fluorescence properties have certain advantages in tumor detection and diagnosis, while fluorescent nanoparticles (FNs) have better photostability and versatility, and perform well in cell imaging and biomolecular sensing. Unlike ordinary fluorescent probes, fluorescent nanoparticles usually have low cytotoxicity, and surface functionalized (antibodies, ligands or enzymes) NPs can be used in biosensors to analyze target proteins. Therefore, the photostability of fluorescent nanoparticles is significantly better than that of small molecule probes. Fluorescent nanoparticles have attracted widespread attention due to their good fluorescence properties and excellent potential in bioimaging. However, the stability and construction methods of fluorescent nanoparticles are also interesting challenges for the application of such materials.

[0004] In view of this, the present invention reports a bimacrocyclic host molecule DNPB based on pillar[5]arene, which contains two rigid macrocyclic cavities with different electronic structures, and can be assembled step by step with different guests according to their respective structural characteristics, thereby constructing a supramolecular functional system with richer performance. First, an alkyl chain with a nitrile group is introduced at both ends of the guest G1, so that the guest G1 can enter the pillar[5]arene cavity. Secondly, the functional guest G2 is a derivative of NDI, and its strong electron-deficient system enables it to combine with the side macrocycle of the bimacrocyclic DNPB. At this point, the bimacrocyclic host DNPB is assembled with guests G1 and G2 at the same time to form a cross-linked supramolecular functional system HG1G2. On this basis, the obtained supramolecular assembly system HG1G2 has good photoluminescence and photochromic properties. Due to the steric hindrance and encapsulation effect based on the step-by-step assembly of the bimacrocyclic, the free radical emission characteristics of HG1G2 are significantly improved, and the fluorescence quantum yield is 3 times that of G2 alone. HG1G2 has excellent photoluminescence and photochromic properties. It is also introduced into polymethyl methacrylate here to make the photochromic and photoluminescence processes more stable in solid systems. It has been successfully applied to the development of information encryption materials. In addition, the presence of cavities of different dimensions can simultaneously increase the dimensions of the main assembly, and then assemble supramolecular polymers through non-proton interactions, hydrogen bonds, metal coordination, etc. of different dimensions. In addition, the present invention uses an orthogonal self-assembly method based on host-guest interactions and metal-ligand interactions to introduce different metal ions (silver, lead, zinc) into the host-guest assembly system to construct a series of in-situ defined supramolecular polymer-based fluorescent nanoparticles (FSNPs). At the same time, the fluorescent nanoparticles have low cell toxicity and can be well used in cell imaging. Summary of the invention

[0005] The object of the present invention is to provide a bimacrocyclic molecule based on pillar[5]arene which can provide two macrocyclic cavities and a method for synthesizing the same.

[0006] Another object of the present invention is to provide a supramolecular host-guest assembly system constructed based on bimacrocyclic molecules of pillar[5]arene and its application as photoluminescent and photochromic materials in information encryption materials.

[0007] Another object of the present invention is to provide supramolecular fluorescent nanoparticles constructed from bimacrocyclic molecules based on pillar[5]arene and apply them to cell imaging.

[0008] 1. Bimacrocyclic chemical sensor DNPB and its synthesis The synthesis method of the bimacrocyclic DNPB of the present invention comprises the following steps: dissolving terephthaloyl chloride in dichloromethane, then dropping the mixture into a dichloromethane system in which bis-N-(2-aminoethyl)-2-(hexylmercapto)acetamide functionalized pillar[5]arene is dissolved, reacting the mixture at 25-30°C for 45-50 hours, removing the solvent to obtain a crude product, and then recrystallizing the crude product with ethanol to obtain a bimacrocyclic molecule based on pillar[5]arene. The molar ratio of bis-N-(2-aminoethyl)-2-(hexylmercapto)acetamide functionalized pillar[5]arene to terephthaloyl chloride is 1.2:1-1.3:1.

[0009] The molecular formula of the synthesized bimacrocyclic chemical sensor DNPB is: 71 H 88 N4O 14 S2, labeled as DNPB, has the structural formula: The mass spectrum and hydrogen spectrum of the dual macrocyclic chemical sensor molecule DNPB are shown in Figure 1 and Figure 2 .

[0010] 2. Construction of a double-macrocyclic DNPB supramolecular host-guest assembly system and its application in information hierarchical encryption 1. Construction method of double macrocyclic DNPB supramolecular host-guest assembly system Using DMSO as solvent, at room temperature, the concentration of 1 × 10 -4 0.5 equivalent of guest G1 with nitrile alkyl chains at both ends was added to the bimacrocyclic main body DNPB of M, and guest G1 entered the pillar aromatic cavity to construct the host-guest complex of HG1. In addition, 1 equivalent of guest G2 was added to the above system. NDI derivative guest G2, as a strong electron-deficient system, enabled it to combine with the side macrocycle of the bimacrocyclic DNPB to form a cross-linked supramolecular functional system HG1G2.

[0011] The structural formula of guest G1 is: The structural formula of guest G2 is: .

[0012] like Figure 3As shown in the figure, the peak shift of the hydrogen spectrum of the assembly of the dimacrocyclic DNPB indicates that when the dimacrocyclic DNPB, guests G1 and G2 exist at the same time, guest G1 enters the column [5] aromatic cavity of the dimacrocyclic DNPB, while guest G2 assembles with the side cavity of the dimacrocyclic DNPB. The above research results show that guest G1 enters the column [5] aromatic cavity of the dimacrocyclic DNPB through CH···π, hydrogen bonding and other interactions, while guest G2 assembles with the side cavity of the dimacrocyclic DNPB through weak interactions such as hydrogen bonding and π···π, and then guest G2 is enclosed in the side cavity, and a supramolecular host-guest assembly system (HG1G2) is assembled.

[0013] 2. Optical properties of the host-guest assembly system of dual macrocyclic DNPB We discussed the photophysical properties of the host-guest assembly system HG1G2 in DMF and the effect of the construction of the host-guest assembly system on the luminescence intensity. When the molar ratio of the bimacrocyclic host molecule DNPB: guest molecule G1: guest molecule G2 was 2:1:2 (1× 10 -4 When the host-guest assembly system HG1G2 was combined with 365 nm UV light, the fluorescence intensity gradually increased with the increase of UV light irradiation time, reaching a maximum value at about 2.75 minutes of irradiation, and showing a strong yellow emission at 575 nm ( Figure 4 ). Figure 4 As shown in Figure d, the UV-visible absorption spectrum of the host-guest assembly system HG1G2 shows three new absorption peaks at 475 nm, 600 nm and 755 nm after irradiation with a 365 nm UV lamp, which may be due to the generation of NDI anion radicals. This may be mainly due to the steric hindrance in the polymer constructed by the host-guest interaction in the host-guest assembly system HG1G2, which prevents the aggregation and annihilation of the NDI anion radicals reduced by the guest molecule G2.

[0014] 3. Analysis of photochromic and photoluminescent luminescence mechanism In order to determine the reasons for the photochromic and photoluminescent emission of the host-guest assembly system HG1G2, electron paramagnetic resonance (EPR) was used to further characterize the host-guest assembly system HG1G2 after 365 nm ultraviolet light irradiation. Figure 5 As shown, EPR detected a g A strong signal with a factor of 2.0037 confirmed the presence of NDI radical anion (NDI ·-), indicating that the emission should come from free radical emission. In addition, we also tested the electron paramagnetic resonance (EPR) of the guest molecule G2 in DMF. Similarly, after irradiation with 365nm ultraviolet light, a corresponding signal was generated at the same position of the EPR spectrum, but its intensity was weaker than that of the host-guest assembly system HG1G2. DMF is an electron donor and G2 (NDI) is an electron acceptor. There is a very strong lone pair electron-π interaction between the electron donor DMF and the electron acceptor G2 (NDI) in the solution. Based on this, we speculate that after 365nm light irradiation, the lone pair electron-π interaction is used as the electron transfer channel from the electron donor DMF to the electron acceptor G2 (NDI), realizing the electron transfer of the lone pair electrons of DMF to the electron-deficient acceptor G2. At the same time, due to the generation of NDI free radical anions, new absorption peaks appear in its ultraviolet-visible absorption spectrum and the color of the solution changes from colorless to brown, which can be seen by the naked eye. In addition, the fluorescence quantum yield (QY) and lifetime of the host-guest assembly system HG1G2 were 26% and 11.31 ns, respectively ( Figure 5 a and 5b). It is worth noting that the QY of the guest molecule G2 system after 365 nm UV illumination is 10%, and the QY of the host-guest assembly system HG1G2 is about 2.6 times higher than that of the guest molecule G2 system. This result shows that compared with the guest molecule G2 system, the host-guest assembly system HG1G2 has an effective protective effect on the luminescence of NDI free radicals. The experimental results show that the supramolecular interaction between molecules and the steric hindrance generated by the host-guest assembly play an important role in enhancing the emission of free radicals.

[0015] 4. Step-by-step assembly of the bimacrocyclic molecule DNPB to construct a host-guest assembly system for information encryption materials The bimacrocyclic DNPB host-guest assembly system (HG1G2) was doped with polymethyl methacrylate at 2wt% using DMF solution to prepare a polymer film. Figure 6As shown in the figure, the film of the host-guest assembly system and the blank PMMA film are combined into an anti-counterfeiting structure in the form of a code. Since both the film of the host-guest assembly system and the blank PMMA film are colorless, the corresponding information cannot be displayed before 365 nm light irradiation. However, after being treated with 365 nm light for 10 seconds, the film of the host-guest assembly system turns light brown, while the blank PMMA film remains colorless, and the information emerges. At the same time, the fluorescence color of the film of the host-guest assembly system turns purple-red, while the blank PMMA film remains blue, and the information emerges. Continue to irradiate with 365 nm light for 10 seconds, the light brown color of the film pattern of the host-guest assembly system deepens, and at the same time, the fluorescence changes from purple-red to orange, while the blank PMMA film remains unchanged, thus completing the secondary encryption. Continue to treat under 365 nm light for 40 seconds, the brown color of the film pattern of the host-guest assembly system deepens, and at the same time, the fluorescence changes from orange to yellow, thus completing the tertiary encryption. Using these materials for information encryption is more convenient than using crystalline materials that are not conducive to processing.

[0016] 3. Construction of supramolecular fluorescent nanoparticles and their application in cell imaging 1. Construction of supramolecular fluorescent nanoparticles using the host-guest assembly system (HG1G2) of dual-macrocyclic DNPB The self-assembly behavior of the bimacrocyclic DNPB and guest molecules G1 and G2 in dimethyl sulfoxide / water (v:v = 9:1) was further studied using scanning electron microscopy. Figure 7 As shown in the figure, the host-guest complex HG1G2 appears an ordered nanocube structure in DMSO / H2O (v:v = 9:1), indicating that the supramolecular host-guest assembly system HG1G2 self-assembles into ordered nanocubes. 3.00 equivalents of metal ions (Ag + , Pb 2+ , Zn 2+ ) after orthogonal self-assembly, such as Figure 7 As shown in the figure, the morphology of the system changes from nanocubes to 3D nanofibers, helical nanorods and cross-linked networks. This morphological transformation can be attributed to the interaction between the supramolecular host-guest assembly system HG1G2 and metal ions (Ag + , Pb 2+ , Zn 2+ ) occurs coordination effect.

[0017] 2. Study on the photophysical properties of supramolecular fluorescent nanoparticles constructed with bimacrocyclic DNPB The UV-visible absorption spectrum and fluorescence emission spectrum were used to investigate. Figure 8As shown in Figure 2, the UV-visible spectrum of the supramolecular host-guest assembly system HG1G2 in DMSO / H2O (v:v=9:1) has absorption peaks at 292, 358, and 378 nm, respectively. + When the absorption spectrum of the supramolecular host-guest assembly system HG1G2 in DMSO / H2O (v:v=9:1) did not change significantly. + The molecular host-guest assembly system HG1G2 (Ag + ⊂HG1G2) solution was added with 10 equivalents of I - , the solution changed from clear and transparent to turbid, and a new absorption band was observed at 420 nm. The ratio of the 0-0 peak to the 0-1 peak of the characteristic absorption double peak of guest G2 at 358 and 378 nm changed from 1.13 to 1.04, which indicated that the supramolecular host-guest assembly system HG1G2 and AgI were obviously assembled. The fluorescence emission spectrum of the supramolecular host-guest assembly system HG1G2 in DMSO / H2O (v:v=9:1) has a maximum emission at 330 nm, and its fluorescence quantum yield is 4% ( Figure 8 ), the fluorescence lifetime is 2.14 ns. 3.00 equivalents of Ag were added to the supramolecular host-guest assembly system HG1G2. + After that, the fluorescence emission spectrum showed a broad emission peak centered at 479 nm, which was attributed to the Ag + Coordination with the host-guest assembly system HG1G2. + 10.0 equivalents of I - , a strong emission band was observed in the range of 380-652 nm, which led to very strong blue emission with a fluorescence quantum yield of 28% and a fluorescence lifetime of 7.25 ns. Thus, we obtained AgI@HG1G2 fluorescent nanoparticles. According to similar operations, PbS@HG1G2 and ZnS@HG1G2 fluorescent nanoparticles based on supramolecular polymers were obtained.

[0018] 3. Step-by-step, orthogonal assembly of bimacrocyclic DNPB molecules to construct fluorescent nanoparticles for cell imaging AgI@HG1G2, PbS@HG1G2, and ZnS@HG1G2 FSNPs based on fluorescent supramolecular polymer networks were used for living cell imaging. Fig. 9As shown in the figure, AgI@HG1G2, PbS@HG1G2 and ZnS@HG1G2FSNPs with a concentration of 20 μM were respectively applied to HepG2 cells for 6 hours, and the distribution of the fluorescent polymer network in the cytoplasm was observed by laser confocal scanning microscopy. Green fluorescence ( Fig. 9 ). These results indicate that AgI@HG1G2, PbS@HG1G2, and ZnS@HG1G2 FSNPs based on fluorescent supramolecular polymer networks can be successfully applied in the field of cell imaging.

[0019] In summary, the present invention synthesized a bimacrocyclic host molecule DNPB based on pillar[5]arene, which contains two rigid macrocyclic cavities with different electronic structures. These cavities can be assembled with different guests in steps according to their respective structural characteristics to construct a supramolecular functional system with richer performance. Due to the steric hindrance and encapsulation effect provided by the bimacrocyclic assembly, the free radical emission characteristics of HG1G2 are significantly improved. At the same time, by utilizing the good photoluminescence and photochromic properties of the supramolecular assembly system HG1G2, it is introduced into polymethyl methacrylate, making the photochromic and photoluminescence processes more stable in the solid system, and it is applied to hierarchical information encryption. In addition, by utilizing the cavities of different dimensions of the bimacrocyclic DNPB of pillar[5]arene, different metal ions (silver, lead, zinc) are introduced into the host-guest assembly system through the orthogonal self-assembly method of host-guest interaction and metal coordination interaction, a series of in situ confined supramolecular polymer-based fluorescent nanoparticles (FSNPs) are constructed, and they are applied to cell imaging. Therefore, the strategy of constructing luminescent materials by step-by-step, orthogonal assembly of bimacrocyclic host compounds is a novel and feasible approach. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] Figure 1 is the mass spectrum of the bimacrocyclic molecule DNPB of the present invention; Figure 2 is the hydrogen spectrum of the bimacrocyclic molecule DNPB of the present invention; Figure 3 This is the host-guest H NMR spectrum of the dual-guest assembly of the bimacrocyclic molecule DNPB of the present invention; Figure 4 This is a photophysical property diagram of the dual-guest assembly system (HG1G2) of the dual-macrocyclic molecule DNPB of the present invention under 365 nm ultraviolet light irradiation; Figure 5 The figure is the fluorescence quantum yield, fluorescence lifetime, electron paramagnetic resonance spectrum and electron transfer process schematic diagram of the dual-guest assembly system (HG1G2) of the dual-macrocyclic molecule DNPB of the present invention before and after 365 nm ultraviolet light irradiation; Figure 6The fluorescence emission, ultraviolet absorption spectrum and code encryption process of the polymethyl methacrylate film doped with the double-guest assembly system (HG1G2) of the double-macrocyclic molecule DNPB of the present invention before and after 365 nm ultraviolet light irradiation; Figure 7 Scanning electron microscope and transmission electron microscope characterization images of the dual-guest assembly system (HG1G2) of the dual-macrocyclic molecule DNPB of the present invention, in which metal ions are introduced to construct nanoparticles through orthogonal assembly; Figure 8 The photophysical properties of nanoparticles were constructed by introducing metal ions into the dual-guest assembly system (HG1G2) of the bimacrocyclic molecule DNPB through orthogonal assembly; Fig. 9 Fluorescent nanoparticles were constructed for the dual-guest assembly system (HG1G2) of the dual-macrocyclic molecule DNPB for cell imaging. DETAILED DESCRIPTION

[0021] The preparation of the bimacrocyclic molecule DNPB of the present invention and the application of the host-guest assembly system for information encryption and cell imaging are further described below through specific examples.

[0022] Example 1 Bimacrocyclic molecule DNPB (1) Synthesis of Bis-N-(2-aminoethyl)-2-(hexylmercapto)acetamide Functionalized Column [5] Aromatic Hydrocarbon MP5 (Synthesis method refers to reference T.-T. Huang, J.-F. Chen, Q. Lin, et al., A Novel Fused Bi-Macrocyclic Host for Sensitive Detection of Cr2O7 2- Based on Enrichment Effect. Chin. Chem. Lett. 2024, 35, 109281.): Ethylenediamine (2 mL) was reacted with thioethyl acetate functionalized column [5] aromatic hydrocarbon BAP (1.15 g, 1 mmol) in ethanol (250 mL). The mixture was heated (60°C) in a round-bottom flask for 24 hours and the solvent was removed. MP5 was obtained after filtration and drying as a white solid with a content of 0.91 g, accounting for 89%.

[0023] (2) Synthesis of bimacrocyclic DNPB: terephthaloyl chloride (0.020 g, 0.10 mmol) was dissolved in dichloromethane (250 mL) after dehydration, and then slowly added dropwise to a DCM system in which bis-N-(2-aminoethyl)-2-(thio)acetamide functionalized column [5]arene MP5 (0.14 g, 0.12 mmol) was dissolved, and the mixture was reacted at 25 °C for 48 hours. The solvent was removed to obtain a yellowish crude product, which was then recrystallized from ethanol to obtain pure DNPB (29%).

[0024] The synthetic route is as follows: Example 2 Construction of a host-guest assembly system by step-by-step assembly of the bimacrocyclic molecule DNPB The construction method of the bimacrocyclic DNPB supramolecular host-guest assembly system: DMSO was used as solvent and the concentration was 1 × 10 -4 0.5 equivalent of guest G1 was added to the bimacrocyclic host DNPB of M, and guest G1 entered the cavity of pillar aromatic hydrocarbon to construct the host-guest complex of HG1. In addition, 1 equivalent of guest G2 was added to the above system. NDI derivative guest G2, as a strong electron-deficient system, enabled it to combine with the side macrocycle of bimacrocyclic DNPB to form a cross-linked supramolecular functional system HG1G2.

[0025] The structural formula of guest G1 is: The synthesis of compound G1 is based on the literature: Liu, Y., Shangguan, L., Shi, B., A multi-responsive cross-linked supramolecular polymer network constructed by musselyieldcoordination interaction and pillar[5]arene-based host–guestcomplexation. Chem. Commun. 54 (2018), 12230–12233. The structural formula of guest G2 is: Synthesis of compound G2: 1,4,5,8-naphthalenetetracarboxylic anhydride (2 g, 8 mmol) and glycine (1.5 g, 20 mmol) were added to N,N-dimethylformamide (150 ml) for reaction, the mixture was heated at 120 °C in a round-bottom flask for 24 hours, the crude product was cooled and filtered, and then recrystallized from DMSO.

[0026] Example 3: Step-by-step assembly of bimacrocyclic molecule DNPB to construct host-guest assembly system for information encryption materials Weigh 2 mg of the bimacrocyclic DNPB host-guest assembly system (HG1G2) obtained in Example 2, dissolve it with 98 mg of polymethyl methacrylate powder in DMF solution, and dry it to prepare a polymer film with a host-guest assembly system of 2 wt%. The host-guest assembly system film and the blank PMMA film are combined in the form of a code to form an anti-counterfeiting structure, such as Figure 6 .

[0027] Example 4 Orthogonal assembly of bimacrocyclic molecule DNPB to construct fluorescent nanoparticles for cell imaging Preparation method of AgI@HG1G2 fluorescent nanoparticles: The supramolecular host-guest assembly system HG1G2 obtained in Example 2 was added to the cuvette, and then 3.00 equivalents of metal ions (Ag + ) are mixed for orthogonal self-assembly, and then the orthogonal self-assembly and Ag + 10.0 equivalents of I was added to the coordinated supramolecular host-guest assembly system. - , supramolecular nanoparticles (AgI@HG1G2FSNPs) with a diameter of 3.26 nm were obtained.

[0028] Preparation method of PbS@HG1G2 fluorescent nanoparticles: The supramolecular host-guest assembly system HG1G2 obtained in Example 2 was added to the cuvette, and then 3.00 equivalents of metal ions (Pb 2+ ) are mixed for orthogonal self-assembly, and then the orthogonal self-assembly with Pb 2+ In the coordinated supramolecular host-guest assembly system, 10.0 equivalents of S were added. 2- , supramolecular nanoparticles (PbS@HG1G2FSNPs) were obtained.

[0029] Preparation method of ZnS@HG1G2 fluorescent nanoparticles: The supramolecular host-guest assembly system HG1G2 obtained in Example 2 was added to the cuvette, and then 3.00 equivalents of metal ions (Zn 2+ ) are mixed for orthogonal self-assembly, and then the orthogonal self-assembly and Zn 2+In the coordinated supramolecular host-guest assembly system, 10.0 equivalents of S were added. 2- , supramolecular nanoparticles (ZnS@HG1G2FSNPs) were obtained.

[0030] AgI@HG1G2, PbS@HG1G2, and ZnS@HG1G2 FSNPs based on fluorescent supramolecular polymer networks were used for living cell imaging, such as Fig. 9 shown.

Claims

1. A bimacrocyclic molecule based on pillar[5]arene, having the molecular formula C 71 H 88 N4O 14 S2, structural formula: 。 2. The method for synthesizing a bimacrocyclic molecule based on pillar[5]arene as claimed in claim 1, comprising dissolving terephthaloyl chloride in dichloromethane, then dropping the mixture into a dichloromethane system in which bis-N-(2-aminoethyl)-2-(hexylmercapto)acetamide functionalized pillar[5]arene is dissolved, reacting the mixture at 25-30°C for 45-50 hours, removing the solvent to obtain a crude product, and then recrystallizing the crude product from ethanol to obtain a bimacrocyclic molecule based on pillar[5]arene; The structural formula of bis-N-(2-aminoethyl)-2-(hexylmercapto)acetamide functionalized column[5]arene is: 。 3. The method for synthesizing bimacrocyclic molecules based on pillar[5]arene as claimed in claim 2, characterized in that: The molar ratio of bis-N-(2-aminoethyl)-2-(hexylmercapto)acetamide functionalized column[5] is aromatic hydrocarbon and terephthaloyl chloride is 1.2:1~1.3:

1.

4. The method for constructing a supramolecular host-guest assembly system based on bimacrocyclic molecules of pillar[5]arene as claimed in claim 1, characterized in that: Using DMSO as solvent, at room temperature, guest G1 was added to the bimacrocyclic host DNPB. Guest G1 entered the pillar aromatic cavity to obtain the host-guest complex system HG1. Guest G2 was then added to the system. Guest G2, as a strong electron-deficient system, combined with the side macrocycle of the bimacrocyclic DNPB to form a cross-linked supramolecular functional system HG1G2. The structural formula of guest G1 is: The structural formula of guest G2 is: 。 5. Application of the supramolecular host-guest assembly system constructed by the method as described in claim 4 as photoluminescent and photochromic materials in information encryption materials.

6. The method for constructing supramolecular fluorescent nanoparticles based on bimacrocyclic molecules of pillar[5]arene as claimed in claim 1, characterized in that: The method for preparing supramolecular fluorescent nanoparticles comprises the following steps: (1) Construction of supramolecular functional system HG1G2: Using DMSO as solvent, at room temperature, guest G1 was added to the bimacrocyclic host DNPB. Guest G1 entered the cavity of the pillar aromatic hydrocarbon to obtain a host-guest complex system of HG1. Guest G2 was then added to the system. Guest G2, as a strong electron-deficient system, was combined with the side macrocycle of the bimacrocyclic DNPB to form a cross-linked supramolecular functional system HG1G2. The structural formula of guest G1 is: The structural formula of guest G2 is: ； (2) Construction of supramolecular fluorescent nanoparticles: Introducing metal ions Ag into the supramolecular host-guest assembly system HG1G2 + , Pb 2+ or Zn 2+ After orthogonal self-assembly, I is added to the supramolecular host-guest assembly system coordinated with metal ions. - or S 2- , and supramolecular nanoparticles were obtained.

7. Use of the supramolecular fluorescent nanoparticles constructed by the method as claimed in claim 6 in cell imaging.

Images