Preparation and application of bimacrocyclic molecules and their supramolecular systems based on pillar[5]arene

Abstract

The present invention provides a bimacrocyclic molecule based on pillar[5]arene and the preparation and application of its supramolecular system. The present invention first synthesizes 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 a step-by-step manner according to their respective structural characteristics to construct a supramolecular functional system HG1G2 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, the good photoluminescence and photochromic properties of the supramolecular assembly system HG1G2 are utilized to introduce it into polymethyl methacrylate, making the photochromic and photoluminescence processes more stable in the solid system, and applying it to hierarchical information encryption. In addition, by utilizing the cavities of different dimensions of pillar[5]arene bimacrocyclic DNPB, different metal ions were introduced into the host-guest assembly system through the orthogonal self-assembly method of host-guest interaction and metal coordination interaction to construct a series of in situ confined supramolecular polymer-based fluorescent nanoparticles (FSNPs) and apply them 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. The present invention 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 the supramolecular fluorescent nanoparticles in cell imaging. Background Art

[0002] The development of supramolecular functional materials based on macrocyclic assembly is a novel, intriguing, and promising approach. Using macrocyclic assemblies to construct supramolecular functional materials can achieve functions that are difficult to achieve with single molecules. For example, the macrocyclic cavity can be used to enclose compatible guests, thereby enabling assembly, stimulus-responsiveness, and controlled release, properties that have broad applications in the construction of advanced smart materials. Based on this, researchers have developed a series of advanced functional materials based on macrocyclic hosts, demonstrating promising performance in host-guest recognition, separation, controlled drug release, catalysis, and other fields. However, traditional assembly processes are limited by the single cavity of the macrocycle, and its host-guest assembly model also has certain limitations. Therefore, improving the assembly capabilities of macrocyclic compounds and developing supramolecular systems with specific functions has always been a major challenge. Double macrocycles can provide cavities of different sizes and electronic structures and can be assembled with different guests, resulting in a richer range of host-guest properties.

[0003] Optical materials, as important functional materials, have been widely used in various fields of production and life. Organic light-emitting free radicals (OLEDs) have become a hot topic of research due to their unique molecular structure and hold great potential for application in the field of luminescence. However, organic free radicals are generally unstable due to their open-shell structure, making their stabilization a challenging task. Therefore, leveraging supramolecular interactions to achieve stable and efficient free radical emission is an intriguing and challenging endeavor. Furthermore, nanomaterials, due to their unique physical and chemical properties, hold broad application prospects in the biomedical field. Biocompatible and highly fluorescent nanoprobes offer advantages in tumor detection and diagnosis, while fluorescent nanoparticles (FNs) offer improved photostability and versatility, excelling in cell imaging and biomolecular sensing. Unlike conventional fluorescent probes, OLEDs generally exhibit low cytotoxicity, and surface-functionalized NPs (antibodies, ligands, or enzymes) can be used in biosensors to analyze target proteins. Consequently, OLEDs exhibit significantly better photostability than small molecule probes. OLEDs have attracted widespread attention due to their excellent fluorescence properties and potential for 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. It 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 exhibits excellent photoluminescence and photochromic properties. It has been incorporated into polymethyl methacrylate (PMMA), further stabilizing the photochromic and photoluminescent processes in solid systems. This has been successfully applied to the development of information encryption materials. Furthermore, the presence of cavities of varying dimensions can simultaneously increase the dimensionality of the host assembly, allowing for the assembly of supramolecular polymers through diverse aprotic interactions, hydrogen bonding, and metal coordination. Furthermore, this invention utilizes an orthogonal self-assembly approach based on host-guest and metal-ligand interactions to introduce different metal ions (silver, lead, and zinc) into the host-guest assembly system, thereby constructing a series of in situ confined supramolecular polymer-based fluorescent nanoparticles (FSNPs). These fluorescent nanoparticles exhibit low cytotoxicity and are well-suited for cell imaging. Summary of the Invention

[0005] The purpose of the present invention is to provide a bimacrocyclic molecule based on pillar[5]arene that can provide two macrocyclic cavities and a synthesis method thereof.

[0006] Another object of the present invention is to provide a supramolecular host-guest assembly system constructed based on a bimacrocyclic molecule of pillar[5]arene and its application as a photoluminescent and photochromic material 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. Dual Macrocyclic Chemical Sensor DNPB and Its Synthesis

[0009] The synthesis method of the bimacrocyclic DNPB of the present invention comprises dissolving terephthaloyl chloride in dichloromethane, then dripping the mixture into a dichloromethane system in which bis-N-(2-aminoethyl)-2-(hexylmercapto)acetamide functionalized pillar[5]arene is dissolved, reacting 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 molar ratio of bis-N-(2-aminoethyl)-2-(hexylmercapto)acetamide functionalized pillar[5]arene to terephthaloyl chloride is 1.2:1-1.3:1.

[0010] The molecular formula of the synthesized bimacrocyclic chemical sensor DNPB is: C 71 H 88 N4O 14 S2, labeled as DNPB, has the following structural formula:

[0011]

[0012] The mass spectrum and hydrogen spectrum of the double macrocyclic chemical sensor molecule DNPB are shown in Figure 1 and Figure 2 .

[0013] 2. Construction of a double-macrocyclic DNPB supramolecular host-guest assembly system and its application in hierarchical information encryption

[0014] 1. Construction method of double macrocyclic DNPB supramolecular host-guest assembly system

[0015] Using DMSO as solvent, the concentration of 1 × 10 -4 To the bimacrocyclic host DNPB (M), 0.5 equivalents of guest G1, a compound with nitrile alkyl chains at both ends, were added. Guest G1 then entered the pillararene cavity, forming a host-guest complex with HG1. Furthermore, one equivalent of guest G2, a derivative of NDI, was added to the system. This NDI derivative acts as a strongly electron-deficient system, enabling it to bind to the pendant macrocycles of the bimacrocyclic DNPB, forming a cross-linked supramolecular functional system, HG1G2.

[0016] The structural formula of guest G1 is:

[0017]

[0018] The structural formula of guest G2 is:

[0019] .

[0020] like Figure 3As shown in Figure 2, the peak shift of the hydrogen spectrum of the assembly of the dimacrocyclic DNPB indicates that when the dimacrocyclic DNPB, guests G1 and G2 coexist, guest G1 enters the columnar [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 columnar [5] aromatic cavity of the dimacrocyclic DNPB through interactions such as CH···π and hydrogen bonds, while guest G2 assembles with the side cavity of the dimacrocyclic DNPB through weak interactions such as hydrogen bonds and π···π, thereby encapsulating guest G2 in the side cavity and constructing a supramolecular host-guest assembly system (HG1G2).

[0021] 2. Optical properties of the host-guest assembly system of double-macrocyclic DNPB

[0022] 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 the host-guest assembly system M), there was no obvious luminescence in the initial state. However, when the host-guest assembly system HG1G2 was irradiated with 365 nm ultraviolet light, the fluorescence intensity gradually increased with the increase of ultraviolet light irradiation time. The fluorescence intensity reached the maximum at about 2.75 minutes of irradiation, and at the same time, a strong yellow emission was shown at 575 nm ( Figure 4 ).like Figure 4 As shown in Figure d, the UV-visible absorption spectrum of the host-guest assembly system HG1G2 exhibits three new absorption peaks at 475 nm, 600 nm, and 755 nm after irradiation with a 365 nm UV lamp. These peaks are likely due to the generation of NDI anion radicals. This is likely due to steric hindrance within the polymer constructed through host-guest interactions in the host-guest assembly system HG1G2. This steric hindrance prevents the aggregation and annihilation of NDI anion radicals reduced by the guest molecule G2.

[0023] 3. Analysis of photochromism and photoluminescence mechanism

[0024] In order to determine the reasons for the photochromism and photoluminescence of the host-guest assembly system HG1G2, electron paramagnetic resonance (EPR) was used to further characterize the host-guest assembly system HG1G2 after irradiation with 365 nm ultraviolet light. 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 is likely from free radicals. We also measured the electron paramagnetic resonance (EPR) of the guest molecule G2 in DMF. Similarly, upon irradiation with 365 nm UV light, a corresponding signal was generated at the same position in the EPR spectrum, but its intensity was weaker than that of the host-guest assembly HG1G2. DMF acts as an electron donor, and G2(NDI) acts as an electron acceptor. The electron donor DMF and the electron acceptor G2(NDI) exhibit strong lone-pair electron-π interactions in solution. Based on this, we speculate that upon irradiation with 365 nm light, the lone-pair electron-π interaction serves as the electron transfer channel from the electron donor DMF to the electron-deficient acceptor G2, enabling electron transfer from the lone pair of DMF to the electron-deficient acceptor G2. Simultaneously, due to the generation of the NDI radical anion, a new absorption peak appears in its UV-visible absorption spectrum, and the solution color changes visibly from colorless to brown. 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 b). Notably, the QY of the guest molecule G2 system after 365 nm UV illumination was 10%, while the QY of the host-guest assembly HG1G2 was approximately 2.6 times higher than that of the guest molecule G2 system. This result indicates that the host-guest assembly HG1G2 effectively protects NDI radical luminescence compared to the guest molecule G2 system. These experimental results demonstrate that supramolecular interactions between molecules and the steric hindrance generated by the host-guest assembly play a significant role in enhancing radical emission.

[0025] 4. Step-by-step assembly of the bimacrocyclic molecule DNPB to construct a host-guest assembly system for information encryption materials

[0026] The double macrocyclic molecule DNPB host-guest assembly system (HG1G2) was doped with polymethyl methacrylate at 2 wt% using DMF solution to prepare a polymer film. Figure 6As shown, a host-guest assembly system film and a blank PMMA film are combined to form an anti-counterfeiting structure in the form of a code. Since both the host-guest assembly system film and the blank PMMA film are colorless, they cannot display the corresponding information before irradiation with 365 nm light. However, after irradiation with 365 nm light for 10 seconds, the host-guest assembly system film turns light brown, while the blank PMMA film remains colorless, revealing the corresponding information. Simultaneously, the fluorescence color of the host-guest assembly system film changes to purple-red, while the blank PMMA film remains blue, revealing the corresponding information. Further irradiation with 365 nm light for 10 seconds deepens the light brown color of the host-guest assembly system film pattern, while its fluorescence changes from purple-red to orange, while the blank PMMA film remains unchanged, thus completing the secondary encryption. Further irradiation with 365 nm light for 40 seconds deepens the brown color of the host-guest assembly system film pattern pattern, while its fluorescence changes from orange to yellow, thus completing the tertiary encryption. Using these materials for information encryption is more convenient than using crystalline materials, which are difficult to process.

[0027] 3. Construction of supramolecular fluorescent nanoparticles and their application in cell imaging

[0028] 1. Construction of supramolecular fluorescent nanoparticles using a host-guest assembly system (HG1G2) of a double-macrocyclic DNPB

[0029] 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 Figure 2, 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+ ) undergoes coordination.

[0030] 2. Study on the photophysical properties of supramolecular fluorescent nanoparticles constructed with double-macrocyclic DNPB

[0031] The UV-visible absorption spectrum and fluorescence emission spectrum were used to investigate. Figure 8 As shown in the figure, 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 supramolecular host-guest assembly system HG1G2 is in DMSO / H2O (v:v=9:1), the absorption spectrum does 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 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 doublet of guest G2 at 358 and 378 nm changed from 1.13 to 1.04, indicating that the supramolecular host-guest assembly system HG1G2 and AgI underwent significant assembly. 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 was added to the supramolecular polymer solution - A strong emission band was observed in the range of 380-652 nm, which resulted in 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. Similar operations were used to obtain PbS@HG1G2 and ZnS@HG1G2 fluorescent nanoparticles based on supramolecular polymers.

[0032] 3. Step-by-step, orthogonal assembly of the bimacrocyclic DNPB molecule to construct fluorescent nanoparticles for cell imaging

[0033] AgI@HG1G2, PbS@HG1G2, and ZnS@HG1G2 FSNPs based on fluorescent supramolecular polymer networks were used for living cell imaging. Figure 9As shown in the figure, the fluorescent supramolecular polymer networks AgI@HG1G2, PbS@HG1G2 and ZnS@HG1G2FSNPs with a concentration of 20 μM were respectively treated with HepG2 cells for 6 hours, and the distribution of the fluorescent polymer networks in the cytoplasm was observed by laser confocal scanning microscopy. Green fluorescence ( Figure 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.

[0034] In summary, the present invention synthesizes 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 step by step with different guests according to their respective structural characteristics, thus constructing 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 applying it 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, to construct a series of in situ confined fluorescent nanoparticles (FSNPs) based on supramolecular polymers, and apply them 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

[0035] Figure 1 This is the mass spectrum of the bimacrocyclic molecule DNPB of the present invention;

[0036] Figure 2 This is the hydrogen spectrum of the bimacrocyclic molecule DNPB of the present invention;

[0037] Figure 3 This is the host-guest H NMR spectrum of the dual-guest assembly of the bimacrocyclic molecule DNPB of the present invention;

[0038] 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;

[0039] Figure 5The figure shows the fluorescence quantum yield, fluorescence lifetime, electron paramagnetic resonance spectrum, and electron transfer process 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;

[0040] Figure 6 The fluorescence emission, UV absorption spectrum and code encryption process of the polymethyl methacrylate film doped with the dual-guest assembly system (HG1G2) of the dual-macrocyclic molecule DNPB of the present invention before and after 365 nm UV irradiation;

[0041] Figure 7 Scanning electron microscopy and transmission electron microscopy 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;

[0042] 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;

[0043] Figure 9 Fluorescent nanoparticles were constructed for the dual-guest assembly system (HG1G2) of the dimacrocyclic molecule DNPB for cell imaging. DETAILED DESCRIPTION

[0044] The following is a further description of 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 through specific examples.

[0045] Example 1 Bimacrocyclic molecule DNPB

[0046] (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]arene 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 by filtration and drying as a white solid with a content of 0.91 g (89%).

[0047] (2) Synthesis of bimacrocyclic DNPB: Terephthaloyl chloride (0.020 g, 0.10 mmol) was dissolved in dichloromethane (250 mL) after dehydration. The solution was then slowly added dropwise to a DCM system containing bis-N-(2-aminoethyl)-2-(hexylthio)acetamide functionalized column[5]arene MP5 (0.14 g, 0.12 mmol). The reaction was carried out 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%).

[0048] The synthetic route is as follows:

[0049]

[0050]

[0051] Example 2 Construction of a host-guest assembly system using a bimacrocyclic molecule DNPB in a step-by-step assembly process

[0052] The construction method of the double macrocyclic DNPB supramolecular host-guest assembly system was as follows: DMSO was used as solvent and the concentration of 1 × 10 -4 0.5 equivalents of guest G1 were added to the bimacrocyclic host DNPB, which then entered the pillararene cavity, forming a host-guest complex with HG1. Furthermore, 1 equivalent of guest G2 was added to the system. The NDI derivative guest G2, acting as a strongly electron-deficient system, enabled it to bind to the side macrocycles of the bimacrocyclic DNPB, forming a cross-linked supramolecular functional system, HG1G2.

[0053] The structural formula of guest G1 is:

[0054]

[0055] The synthesis of compound G1 is based on the following 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.

[0056] The structural formula of guest G2 is:

[0057]

[0058] 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). 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.

[0059] Example 3: Step-by-step assembly of bimacrocyclic molecule DNPB to construct a host-guest assembly system for information encryption materials

[0060] Weigh 2 mg of the bimacrocyclic DNPB host-guest assembly system (HG1G2) obtained in Example 2 and dissolve it with 98 mg of polymethyl methacrylate powder in DMF solution. Dry it to form a polymer film with a 2 wt% host-guest assembly system. The host-guest assembly system film and a blank PMMA film are combined in the form of a code to form an anti-counterfeiting structure, such as Figure 6 .

[0061] Example 4 Orthogonal assembly of bimacrocyclic molecules DNPB to construct fluorescent nanoparticles for cell imaging

[0062] Preparation method of AgI@HG1G2 fluorescent nanoparticles:

[0063] 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 is combined with Ag + 10.0 equivalents of I was added to the coordinated supramolecular host-guest assembly system. - , and obtained supramolecular nanoparticles (AgI@HG1G2FSNPs) with a diameter of 3.26 nm.

[0064] Preparation method of PbS@HG1G2 fluorescent nanoparticles:

[0065] 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+ 10.0 equivalents of S were added to the coordinated supramolecular host-guest assembly system. 2- , and obtained supramolecular nanoparticles (PbS@HG1G2FSNPs).

[0066] Preparation method of ZnS@HG1G2 fluorescent nanoparticles:

[0067] 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 with Zn 2+ 10.0 equivalents of S were added to the coordinated supramolecular host-guest assembly system. 2- , and obtained supramolecular nanoparticles (ZnS@HG1G2FSNPs).

[0068] AgI@HG1G2, PbS@HG1G2, and ZnS@HG1G2 FSNPs based on fluorescent supramolecular polymer networks were used for living cell imaging, e.g. Figure 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 according to claim 1, wherein terephthaloyl chloride is dissolved in dichloromethane, and then the mixture is added dropwise to a dichloromethane system in which bis-N-(2-aminoethyl)-2-(hexylmercapto)acetamide functionalized pillar[5]arene is dissolved, and the mixture is reacted at 25-30°C for 45-50 hours, the solvent is removed to obtain a crude product, and the crude product is recrystallized 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 a bimacrocyclic molecule based on pillar[5]arene according to claim 2, characterized in that: The molar ratio of bis-N-(2-aminoethyl)-2-(hexylmercapto)acetamide functionalized column[5]arene to terephthaloyl chloride is 1.2:1~1.3:

1.

4. The method for constructing a supramolecular host-guest assembly system based on a bimacrocyclic molecule of pillar[5]arene according to claim 1, characterized in that: Using DMSO as solvent, at room temperature, guest G1 was added to the bimacrocyclic molecule based on pillar[5]arene. Guest G1 entered the cavity of pillar[5]arene to obtain a host-guest complex system of HG1. Guest G2 was then added to the host-guest complex system of HG1. Guest G2, as a strong electron-deficient system, combined with the side macrocycle of the bimacrocyclic molecule based on pillar[5]arene 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 according to claim 4 as a photoluminescent and photochromic material in information encryption materials.

6. The method for constructing supramolecular fluorescent nanoparticles based on bimacrocyclic molecules of pillar[5]arene according to 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 molecule based on pillar[5]arene. Guest G1 entered the cavity of pillar[5]arene to obtain a host-guest complex system of HG1. Guest G2 was then added to the host-guest complex system of HG1. Guest G2, as a strong electron-deficient system, was combined with the side macrocycle of the bimacrocyclic molecule based on pillar[5]arene 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 was added to the supramolecular host-guest assembly system coordinated with metal ions. - or S 2- , and obtained supramolecular fluorescent nanoparticles.

7. Use of the supramolecular fluorescent nanoparticles constructed by the method according to claim 6 in cell imaging for non-diagnostic and therapeutic purposes.

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