Preparation method and application of anion coordination driven hierarchical self-assembly gel for molecular separation and electric sensing

Abstract

The invention relates to the field of supramolecular gel synthesis, and provides a ligand (LNH2, LUPy) which takes triphenylbenzene as a central connector and has an amino group or an Upy unit at the tail end, a complex (HNH2, HUPy) which can be formed by self-assembling the ligand and phosphate anions in an acetonitrile solution and has a helical structure, and supramolecular gel formed by volatilizing the complex through acetonitrile or swelling chloroform. The gel provided by the invention can be used as a stationary phase to realize host-guest separation under a solid-liquid phase, and the gel has excellent conductivity, so that the host-guest separation of the gel can be monitored in real time through an electric sensing method, and a new method and thought are provided for researching host-guest properties in supramolecular chemistry.

Description

Technical Field

[0001] The invention relates to the field of supramolecular gel synthesis, in particular to a preparation method and application of anion coordination-driven hierarchical self-assembly gel for molecular separation and electrical sensing. Background Art

[0002] Host-guest chemistry is a discipline that studies the interactions between host molecules and guest molecules and their functional properties. Host molecules usually have specific cavities or recognition sites that can selectively bind to guest molecules to form stable supramolecular assemblies. As a rapidly developing field in chemistry, host-guest chemistry has been widely used in many frontier fields and interdisciplinary disciplines such as chemical catalysis, molecular separation, environmental science and biological science in recent years. At the same time, the research results of host-guest chemistry have provided strong support for the design of new materials, biomedical research, etc., showing broad application prospects.

[0003] However, traditional host-guest chemistry in solution is ultimately difficult to apply to macroscopic reality. The addition of discrete supramolecular assemblies to gels is expected to achieve solid-liquid host-guest chemistry. The addition of supramolecular assemblies can adjust the porosity of the gel and give the gel the ability to selectively encapsulate and release guests. Therefore, in recent years, researchers have begun to try to dope organic macrocycles or molecular cages with common stationary phase substances such as ion exchange resins and alumina to achieve solid-liquid host-guest chemistry. However, the use of gels formed by independent cage-structured substances as stationary phases to capture and release compounds from a mixture with high selectivity remains to be explored.

[0004] Anion coordination with similar coordination mode to metal cations shows good biocompatibility due to the presence of its multiple hydrogen bond system. In recent years, the field of anion coordination self-assembly has gradually developed and matured, and a variety of supramolecular assemblies including triple helix, tetrahedron, triangular bipyramid, octahedron, etc. have been successfully constructed. In 2022, the first work on the formation of viscoelastic conductive gel by anion coordination assembly was reported (Gao, Y., et al. Hierarchical self-assembly of adhesive and conductive gels with anion-coordinated triplehelicate junctions, Angew. Chem. Int. Ed. 2022, 61, e202201793). However, the gel formed by discrete anion coordination groups as the stationary phase for host-guest chemistry in the mobile phase still has the difficulty of being easily decomposed in solution. Summary of the invention

[0005] In this application, ligands (L NH2 , L UPy ) with triphenylbenzene as the central linker and amino or Upy units at the ends were designed and synthesized. Self-assembly of these ligands with phosphate anions in an acetonitrile solution can form complexes (H NH2 , H UPy ) with a helical structure. The complexes can form supramolecular gels by acetonitrile evaporation or chloroform swelling. Such gels can be used as a stationary phase to selectively encapsulate choline (Ch + ) from a mixed solution of choline (Ch + ) and N,N-dimethylethanolamine (DMEA); subsequently, by adding the competitive guest trimethylpropylamine (N + 1113 + + ) of Ch + to the gel, the encapsulated Ch

[0006] can be released. In addition, the above host-guest properties of the gel can be monitored in real time by an electro-sensing method, which provides a new method and idea for studying host-guest properties in supramolecular chemistry.

[0007] The gel described in the present invention is based on a helical structure, which is formed by self-assembly of a ligand with triphenylbenzene as the central linker and amino or Upy units at the ends with phosphate anions in an acetonitrile solution. The helical structure forms a supramolecular gel by acetonitrile evaporation or chloroform swelling.

[0008] The supramolecular gel included in the present invention is prepared by the following preparation method:

[0009] S3.1 Preparation of the anionic ligand L NH2 :

[0010] S3.11 Dilute (Boc)2O with tetrahydrofuran, slowly drop the diluted solution into the tetrahydrofuran solution of a, react for twelve hours under an ice bath, stir the reaction solution with silica gel after the reaction is completed, use a eluent of petroleum ether:ethyl acetate = 1:1, separate by silica gel column chromatography, collect the corresponding product solution and rotary evaporate, obtain a light yellow powdery substance, dry it with an oil pump to obtain compound b;

[0011] S3.12 Under a nitrogen atmosphere, slowly drop the dichloromethane solution of compound b into the dichloromethane solution of 2-nitroisocyanate, stop the reaction after 4 hours, and filter to obtain compound c;

[0012] S3.13 Under an argon-protected environment, hydrazine hydrate diluted with ethanol was added dropwise to a mixed solution of compound c, Pd / C, and ethanol, and the reaction was carried out at 85 °C for five hours until the reaction solution turned grayish white. The reaction was processed. The sand core was covered with diatomaceous earth, and the Pd / C attached with the product was left on the upper layer of the sand core. The filter cake was dissolved in N,N-dimethylformamide, and then the palladium carbon was filtered off with diatomaceous earth. The obtained filtrate was rotary evaporated and then water was added to precipitate white solid d. The solid was filtered by suction, washed with ether, and dried under vacuum to obtain compound d;

[0013] S3.14 Compound d was dissolved in tetrahydrofuran and N,N-dimethylformamide. After dissolution, 4-nitrophenyl isocyanate was dissolved in tetrahydrofuran and added dropwise to the reaction solution. The mixture was heated and stirred. It was observed that yellow products gradually precipitated. The reaction was carried out overnight. The reaction solution was rotary evaporated, and a poor solvent, ether, was added to precipitate yellow solid. The solid was filtered by suction and dried under vacuum to obtain compound e;

[0014] S3.15 Compound e was placed in dichloromethane, and trifluoroacetic acid was slowly added dropwise thereto at room temperature. The reaction solution gradually became clear. The reaction was carried out for twelve hours. Saturated NaOH solution was added to the reaction solution until the reaction solution was neutral. The reaction solution gradually became turbid, and yellow solid precipitated. The solid was filtered by suction to obtain ligand L NH2 ;

[0015] S3.2 Preparation of ligand L UPy : The ligand L obtained in step S3.15 NH2 was added to N,N-dimethylformamide. H-UPy was dissolved in tetrahydrofuran, and the reaction was carried out under reflux condensation at 85 °C overnight. Solids gradually precipitated. The pale yellow solid was filtered by suction to obtain ligand L UPy ;

[0016] S3.3 Preparation of complex H NH2 : H3PO4 and (TBA)OH were prepared into (TBA)3PO4 in an aqueous solution according to a ratio of 1:1. (TBA)3PO4 was taken and added to the acetonitrile solution of ligand L obtained in step S3.1 NH2 . After stirring at room temperature, a clear solution was obtained. The solution was filled into a glass tube and placed in a large bottle containing ether. After slow diffusion for about seven days, solid H was obtained NH2 ;

[0017] S3.4 Preparation of complex H UPy : H3PO4 and (TBA)OH were prepared into (TBA)3PO4 in an aqueous solution according to a ratio of 1:1. (TBA)3PO4 was taken and added to the acetonitrile solution of ligand L obtained in step S3.2 UPy . After stirring at room temperature, a clear solution was obtained. The solution was filled into a glass tube and placed in a large bottle containing ether. After slow diffusion for about seven days, solid H was obtained UPy ;

[0018] S3.5 Acetonitrile evaporation to form gel: Dissolve the solid powder of the complex H NH2 or H Upy prepared in step S3.3 or S3.4 in an acetonitrile solution, and slowly evaporate the solvent to gradually increase its concentration, finally obtaining the supramolecular gel G NH2 or G Upy ;

[0019] S3.6 Chloroform swelling to form gel: Immerse the solid powder of the complex H NH2 or H Upy prepared in step S3.3 or S3.4 in a chloroform solution, finally obtaining the supramolecular gel G NH2 or G Upy .

[0020] A further method for optimizing the preparation of the gel is that the compound for performing step S3.15 and subsequent steps is the compound d obtained in step S3.13 prepared by the preparation method of steps S3.12 - S3.14.

[0021] The supramolecular gel included in the present invention, the storage modulus value of the gel formed by the UPy complex is greater than the storage modulus value of the amino terminus, and the storage modulus value and loss modulus value of the gel obtained by cycling the method of step S3.12 are greater than those of the gel obtained by the non - cycling method and the values are relatively stable.

[0022] The supramolecular gel included in the present invention, the gel can be used as a stationary phase to selectively encapsulate Ch + from the mixed solution of choline Ch - and N,N + dimethyl ethanolamine; then, by adding the competitive guest trimethylpropylamine N + to the gel, the Ch 1113 + encapsulated by the gel + can be released, realizing the host - guest separation application in the solid - liquid phase.

[0023] The supramolecular gel included in the present invention, its host - guest separation application can be monitored in real time by an electrical sensing method.

[0024] Based on the above technical solutions, the present invention aims at the deficiency that the host - guest chemistry in solution state in the existing reported supramolecular chemistry is difficult to be applied to the macroscopic reality, and constructs a helical structure based on phosphate anion coordination. The gel obtained by swelling these helical assemblies with chloroform can be used as a stationary phase to achieve host - guest separation in the solid - liquid phase. At the same time, due to the excellent electrical conductivity of this type of gel, the host - guest separation of the gel can be monitored in real time by an electrical sensing method, which provides a new method and idea for studying the host - guest properties in supramolecular chemistry. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] Figure 1 Synthetic route diagram of the anionic ligand L in Example 1 of the present invention 1-NH2 and L 1-Upy wherein, (1) Di-tert-butyl dicarbonate, tetrahydrofuran, ice bath; (2) 2-Nitroisocyanate, tetrahydrofuran, reflux; (3) Hydrazine hydrate, palladium on carbon (10%), ethanol, reflux; (4) 4-Nitroisocyanate, tetrahydrofuran / N,N-dimethylformamide, reflux; (5) Trifluoroacetic acid, dichloromethane, room temperature; (6) H-UPy, tetrahydrofuran / N,N-dimethylformamide, reflux.

[0026] Figure 2 Synthetic route diagram of the anionic ligand L in Example 2 of the present invention 2-NH2 and L 2-Upy wherein, (4) 2-Nitroisocyanate, tetrahydrofuran / N,N-dimethylformamide, reflux; (5) Hydrazine hydrate, palladium on carbon (10%), ethanol, reflux; (6) 4-Nitroisocyanate, tetrahydrofuran / N,N-dimethylformamide, reflux; (7) Trifluoroacetic acid, dichloromethane, room temperature; (8) H-UPy, tetrahydrofuran / N,N-dimethylformamide, reflux.

[0027] Figure 3 Schematic diagram of the gels G 1-NH2 , G 1-Upy , G 2-NH2 , G 2-UPy obtained by the evaporation of acetonitrile in Examples 1 and 2 of the present invention.

[0028] Figure 4 Schematic diagram of the gels G 1-NH2 , G 1-Upy , G 2-NH2 , G 2-UPy obtained by the swelling of chloroform in Examples 1 and 2 of the present invention.

[0029] Figure 5 Schematic diagrams of the structures of the ligands (L 1-NH2 , L 1-UPy , L 2-NH2 , L 2-UPy ), complexes (H 1-NH2 , H 1-UPy , H 2 -NH2 , H 2-UPy ) and the gelation of the complexes in Examples 1 and 2 of the present invention.

[0030] Figure 6 Schematic diagrams of the gels G 1-NH2 , G 1-UPy , G 2-NH2and G 2-UPy Rheological test chart of

[0031] Figure 7 a)-d) Gel G prepared by acetonitrile volatilization in Examples 1 and 2 of the present invention 1-NH2 and G 1-UPy and G 2-NH2 and G 2-UPy SEM images of 1-NH2 and G 1-UPy and G 2-NH2 and G 2-UPy ; e)-h) SEM images of gel G prepared by chloroform swelling in Examples 1 and 2 of the present invention

[0032] Figure 8 a) Schematic diagram of gel filtration of choline molecules in Examples 1 and 2 of the present invention; b) Line chart of choline concentration in every 500 μL eluent in Examples 1 and 2 of the present invention; c) Histogram of total amount of choline molecules adsorbed by four gels in Examples 1 and 2 of the present invention

[0033] Figure 9 a) Schematic diagram of selective encapsulation and release of choline molecules by gel in Examples 1 and 2 of the present invention; b) NMR spectra corresponding to the gel in Examples 1 and 2 of the present invention

[0034] Figure 10 Gel G in Examples 1 and 2 of the present invention 1-UPy , G 2-UPy , G 1-NH2 , and G 2-NH2 Conductivity and corresponding resistivity charts

[0035] Figure 11 a) Gel N in Examples 1 and 2 of the present invention 1113 + and Ch + and DMEA mixture in CDCl3 solution; b) I-V curve chart of gel DMEA, Ch + and N 1113 + in CDCl3 solution

[0036] Figure 12 a) Schematic diagram of gel conductive device system in Examples 1 and 2 of the present invention; b) Current change chart during the process of gel encapsulation and release of choline molecules in Examples 1 and 2 of the present invention; c) NMR spectra corresponding to the gel in Examples 1 and 2 of the present invention

[0037] Figure 13 Gel G in Example 1 of the present invention 1-UPy Recycling cycle chart

[0038] Figure 14 Gel G of Embodiment 2 of the present invention 2-UPy Recycling cycle diagram. Detailed implementation mode

[0039] Next, the technical solutions in the embodiments of the present invention will be clearly and completely described in conjunction with the accompanying drawings in the embodiments of the present invention. However, this should not be construed as limiting the scope of the above-mentioned subject matter of the present invention to the following embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts shall fall within the scope of protection of the present invention.

[0040] First, the synthesis of H-UPy, referring to the synthesis in the reference (Zhu, B., et al. Thermoreversible supramolecular polyurethanes with self-complementary quadruple hydrogen-bonded end groups, J. Appl. Polym. Sci. 2011, 123, 1755-1763)

[0041] Embodiment 1:

[0042] As Figure 1 shown, the synthesis of the anion ligands L 1-NH2 and L 1-Upy :

[0043] Compound b

[0044] Dilute (Boc)2O (0.6 g, 2.8 mmol) with 4 mL of tetrahydrofuran (THF), and slowly add the diluted solution dropwise to the THF solution (20 mL) of a (1 g, 2.8 mmol). React under an ice bath for twelve hours. Silica gel sample the reaction solution after the reaction is completed, use a eluent of petroleum ether: ethyl acetate = 1:1, separate by silica gel column chromatography, collect the corresponding product solution and rotary evaporate, obtain a pale yellow powdery substance, dry it with an oil pump to obtain product b (680 mg, 52%). 1 1H NMR (400 MHz, DMSO-d6, ppm): δ 9.43 (s, 1H, Ha), 7.68 (d, 2H, H6), 7.56 (d, 2H, H5), 7.55 (s, 1H, H1), 7.48 (d, J = 8.0 Hz, 4H, H3), 6.68 (d, J = 8.0 Hz, 4H, H4), 5.23 (s, 4H, Hb), 1.50 (s, 9H, H6). 1313C NMR (100 MHz, DMSO-d6, ppm): δ 152.8, 148.4, 141.7, 140.8, 139.0, 134.3, 127.7, 127.5, 127.1, 121.3, 121.0, 118.4, 114.2, 79.2, 28.1. ESI-MS m / z, found 474.2594, calculated for C 29 H 29 N3O2 [M+Na] + 474.2151。

[0045] Compound c

[0046] Under a nitrogen atmosphere, a solution of compound b (0.68 g, 1.5 mmol) in dichloromethane (10 mL) was slowly added dropwise to a solution of 2-nitroisocyanate (0.54 g, 3.3 mmol) in dichloromethane (40 mL). After reacting for 4 h, the reaction was stopped, and compound c (1.05 g, 89%) was obtained by suction filtration. 1 1H NMR (400 MHz, DMSO-d6, ppm): δ 10.00 (s, 2H, Hc), 9.65 (s, 2H, Hb), 9.46 (s, 1H, Ha), 8.33 (d, J = 8.0 Hz, 2H, H10), 8.10 (d, J = 8.0 Hz, 2H, H9), 7.82 (m, 4H, H4), 7.79 (d, 3H, H2 / H1), 7.76 (d, J = 8.0 Hz, 2H, H6), 7.72 (d, J = 8.0 Hz, 2H, H8), 7.64 (d, J = 8.0 Hz, 4H, H3), 7.60 (d, J = 8.0 Hz, 2H, H7), 1.50 (s, 9H, H11). 13 13C NMR (100 MHz, DMSO-d6, ppm): δ 152.8, 151.8, 141.2, 141.0, 139.3, 138.9, 137.6, 135.0, 134.9, 134.3, 133.8, 127.5, 127.3, 125.4, 122.9, 122.6, 122.3, 118.9, 118.4, 79.1, 28.1. ESI-MS m / z, found 802.2960, calculated for C43H37N7O8 [M+Na] + 802.2595。

[0047] Compound d

[0048] Under an argon-protected environment, 8 mL of hydrazine hydrate was diluted with 6 mL of ethanol and added dropwise to a mixture of c (1.1 g, 1.41 mmol), 0.11 g of Pd / C, and 20 mL of ethanol. The reaction was carried out at 85 °C. The reaction was carried out for five hours until the reaction solution turned grayish white, and the reaction was treated. The sand core was covered with diatomaceous earth, and the Pd / C attached with the product was left on the upper layer of the sand core. The filter cake was dissolved in N,N-dimethylformamide, and then the palladium carbon was filtered off with diatomaceous earth. The obtained filtrate was rotary evaporated to 1 to 2 mL, water was added, and a white solid d was precipitated. It was filtered by suction, washed with ether, and dried in vacuo to obtain product d (480 mg, 51%). 1 H NMR (400 MHz, DMSO-d6, ppm): δ 9.46 (s, H, Ha), 8.92 (s, 2H, Hb), 7.79 (s, 2H, Hc), 7.77 (m, 11H, H1 / H2 / H4 / H5 / H8), 7.59 (d, J = 8.0 Hz, 4H, H3), 7.38 (d, J = 8.0 Hz, 2H, H9), 6.86 (t, 2H, H7), 6.76 (d, J = 8.0 Hz, 2H, H10), 6.59 (t, 2H, H6), 4.80 (s, 4H, Hd), 1.50 (s, 9H, H11). 13 C NMR (100 MHz, DMSO-d6, ppm): δ 153.1, 152.8, 141.2, 140.9, 139.2, 133.9, 133.3, 127.4, 127.3, 124.7, 124.5, 123.8, 122.6, 118.4, 118.2, 116.8, 115.9, 79.1, 28.1. ESI-MS m / z, found 742.4613, calculated for C43H41N7O4 [M+Na] + 742.3112。

[0049] Compound e

[0050] d (0.48 g, 0.67 mmol) was dissolved in 20 mL of tetrahydrofuran and 1.5 mL of N,N-dimethylformamide. After dissolution, 4-nitrophenyl isocyanate (0.25 g, 1.53 mmol) was dissolved in 2.0 mL of tetrahydrofuran and added dropwise to the reaction solution. The mixture was heated and stirred at 85 °C. It was observed that a yellow product gradually precipitated. The reaction was carried out overnight. The reaction solution was rotary evaporated to 1 to 2 ml, and a poor solvent, ether, was added to precipitate a yellow solid. It was filtered by suction and dried in vacuo to obtain product e (642.8 mg, 92%). 11H NMR (400 MHz, DMSO-d6, ppm): δ 10.09 (s, 2H, He), 9.46 (s, 1H, Ha), 9.39 (s, 2H, Hd), 8.50 (s, 2H, Hc), 8.30 (s, 2H, Hb), 8.19 (d, J = 8.0 Hz, 4H, H10), 7.80 (s, 2H, H2), 7.78 (m, 6H, H4 / H12), 7.74 (d, J = 10.0 Hz, 4H, H5 / H8), 7.72 (d, J = 8.0 Hz, 2H, H9), 7.62 (d, J = 8.0 Hz, 2H, H11), 7.60 (d, J = 8.0 Hz, 4H, H3), 7.57 (s, 1H, H1), 7.13 (m, 4H, H6 / H7), 1.50 (s, 9H, H13). 13C NMR (100 MHz, DMSO-d6, ppm): δ 162.3, 153.1, 152.8, 146.7, 141.1, 140.9, 139.6, 139.2, 133.9, 133.6, 131.8, 130.0, 128.9, 128.2, 127.4, 127.3, 125.2, 124.6, 124.3, 123.7, 123.2, 122.7, 118.4, 117.3, 79.1, 35.8, 30.8, 28.1. ESI-MS m / z, found 1070.5340, calculated for C 57 H 49 N 11 O 10 [M + Na] + 1070.3556. Ligand L 1-NH2 :

[0051] e (0.7 g, 0.67 mmol) was placed in 20 mL of dichloromethane, and trifluoroacetic acid (7 mL) was slowly added dropwise thereto at room temperature. The reaction solution gradually became clear. The reaction was carried out for twelve hours. Saturated NaOH solution was added to the reaction solution until the reaction solution was neutral. The reaction solution gradually became turbid, and yellow solid precipitated. It was filtered by suction to obtain L 1-NH2 (630 mg, 94%). 11H NMR (400 MHz, DMSO-d6, ppm): δ 9.87 (s, 2H, He), 9.23 (s, 2H, Hd), 8.31 (s, 2H, Hc), 8.19 (d, J = 8.0 Hz, 4H, H10), 8.15 (s, 2H, Hb), 7.77 (d, J = 8.0 Hz, 4H, H4), 7.74 (d, J = 8.0 Hz, 4H, H9), 7.70 (s, 2H, H2), 7.67 (s, 1H, H1), 7.59 (d, 4H, H3 / H11), 7.58 (m, 4H, H5 / H12), 7.15 (m, 2H, H6 / H7), 6.73 (d, J = 8.0 Hz, 2H, H8), 5.53 (s, 2H, Ha). 13 13C NMR (100 MHz, DMSO-d6, ppm): δ 153.1, 152.8, 147.8, 146.6, 141.9, 139.4, 133.9, 132.0, 130.3, 128.0, 127.6, 127.4, 125.2, 124.9, 124.8, 124.0, 123.8, 122.0, 121.7, 118.5, 117.4, 114.6. ESI-MS m / z, found 970.4701, calculated for C52H41N11O8 [M+Na] + 970.3021。

[0052] Ligand L 1-UPy :

[0053] L 1-NH2 (100 mg, 0.1054 mmol) was added to 2 mL of N,N-dimethylformamide in a three-necked flask. H-UPy (40.18 mg, 0.137 mmol) was dissolved in 5 mL of tetrahydrofuran, and the reaction was refluxed overnight at 85 °C with condensation. A solid gradually precipitated, and the solid was filtered to obtain a pale yellow solid L 1-UPy (109 mg, 84%). 11H NMR (400 MHz, DMSO-d6, ppm): δ 11.57 (s, 1H, Hi), 9.86 (s, 2H, He), 9.64 (s, 1H, Hh), 9.22 (s, 2H, Hd), 8.54 (s, 1H, H1), 8.30 (s, 2H, Hc), 8.18 (d, J = 8.0 Hz, 4H, H10), 8.14 (s, 2H, Hb), 7.80 (m, 4H, H8 / H2), 7.76 (d, J = 8.0 Hz, 4H, H9), 7.71 (d, J = 8.0 Hz, 4H, H4), 7.68 (d, J = 8.0 Hz, 2H, H12), 7.59 (d, J = 8.0 Hz, 4H, H3), 7.57 (m, 4H, H5), 7.52 (d, J = 8.0 Hz, 2H, H11), 7.36 (s, 1H, Ha), 6.16 (t, 1H, Hg), 5.77 (t, 1H, Hf), 3.12 (m, 4H, H15 / H20), 2.10 (s, 3H, H13), 1.45 (m, 4H, H16 / H19), 1.32 (m, 4H, H17 / H18). 13C NMR (100 MHz, DMSO-d6, ppm): δ 155.2, 154.8, 153.2, 152.8, 146.6, 141.4, 141.0, 140.4, 139.5, 133.7, 132.8, 132.0, 130.3, 127.5, 127.3, 125.2, 124.9, 124.0, 123.8, 122.6, 118.6, 117.9, 117.4, 104.6, 35.8, 29.7, 29.1, 26.1, 23.4. ESI-MS m / z, found 1263.5890, calculated for C 65 H 60 N 16 O 11 [M + Na] + 1263.4519。

[0054] Example 2:

[0055] As Figure 2 shown, synthesis of the anionic ligands L 1-NH2 and L 1-Upy :

[0056] Compound 2e

[0057] Dissolve d (0.7 g, 1 mmol) in 15 mL of tetrahydrofuran and 5 mL of N,N-dimethylformamide. After stirring to dissolve, dissolve 2-nitrobenzene isocyanate (0.36 g, 2.2 mmol) in 2 mL of tetrahydrofuran and slowly add it dropwise to the reaction solution. Stir under heating reaction conditions at 85 °C. Gradually, a yellow product precipitates. Filter by suction and dry under vacuum to obtain product 2e (1.01 g, 96.2%). 1 H NMR (400 MHz, DMSO-d6, ppm): δ 9.77 (s, 2H, He), 9.47 (s, 1H, Ha), 9.30 (s, 2H, Hd), 9.25 (s, 2H, Hc), 8.34 (d, 2H, Hb), 8.12 (d, 2H, H3), 7.86 (s, 2H, H2), 7.78 (m, 10H, H5 / H6 / H7 / H8 / H9), 7.71 (s, 1H, H1), 7.59 (m, 6H, H10 / H11 / H12), 7.43 (d, J = 8.0 Hz, 2H, H13), 7.21 (d, 4H, H4), 7.07 (d, J = 8.0 Hz, 2H, H14), 1.50 (s, 9H, H15). 13 C NMR (100 MHz, DMSO-d6, ppm): δ 153.0, 152.8, 141.1, 139.5, 135.0, 133.8, 133.6, 133.3, 128.6, 127.5, 127.3, 125.7, 125.4, 123.2, 122.6, 122.3, 118.4, 79.1, 28.1. ESI-MS m / z, found 1070.9644, calculated for C 57 H 49 N 11 O 10 [M+Na] + 1070.3556。

[0058] Compound 2f

[0059] Under an argon-protected environment, dilute 5 mL of hydrazine hydrate with 6 mL of ethanol and add it dropwise to a mixture of 2e (0.8 g, 0.8 mmol), 0.08 g of Pd / C, and 20 mL of ethanol. React at 85 °C. React for five hours until the reaction solution turns grayish white, and then treat the reaction. Spread diatomaceous earth on the sintered glass funnel and leave the Pd / C with the attached product on the upper layer of the sintered glass funnel. Dissolve the filter cake in N,N-dimethylformamide and then filter off the palladium carbon with diatomaceous earth. Rotate evaporate the obtained filtrate to 1 to 2 mL, add water to precipitate a white solid, filter by suction, and dry under vacuum to obtain 2f (426 mg, 54%). 11H NMR (400 MHz, DMSO-d6, ppm): δ 9.48 (s, 1H, Ha), 9.26 (s, 2H, Hc), 8.20 (s, 2H, Hd), 8.12 (s, 4H, He / Hb), 7.78 (m, 9H, H1 / H4 / H8 / H14), 7.60 (m, 10H, H2 / H3 / H5 / H13), 7.35 (d, J = 8.0 Hz, 2H, H9), 7.09 (m, 4H, H6 / H7), 6.85 (m, 2H, H11), 6.74 (d, 2H, H12), 6.56 (m, 2H, H10), 4.83 (s, 4H, Hf), 1.50 (s, 9H, H15). 13 13C NMR (100 MHz, DMSO-d6, ppm): δ 153.9, 153.1, 152.7, 152.7, 141.1, 139.7, 139.2, 133.8, 133.5, 131.7, 131.0, 127.4, 127.3, 124.6, 124.4, 124.2, 124.0, 123.0, 122.6, 118.4, 116.7, 115.8, 79.1, 28.1. ESI-MS m / z, found 1010.8494, calculated for C 57 H 53 N 11 O6[M + Na] + 1010.4072。

[0060] Compound 2g

[0061] Dissolve 2f (0.5 g, 0.5 mmol) in 13 mL of tetrahydrofuran and 7 mL of N,N-dimethylformamide. After stirring to dissolve, dissolve 4-nitrobenzene isocyanate (0.25 g, 1.5 mmol) in 2 mL of tetrahydrofuran and slowly add it dropwise to the reaction solution. Stir under heating at 85 °C. Gradually, a yellow product precipitates. Filter by suction and dry in vacuo to obtain 2g (631.2 mg, 96%). 11H NMR (400 MHz, DMSO-d6, ppm): δ 9.91 (s, 2H, Hg), 9.48 (s, 1H, Ha), 9.28 (s, 2H, Hf), 8.52 (s, 2H, He), 8.48 (s, 2H, Hd), 8.32 (s, 2H, Hc), 8.17 (s, 2H, Hb), 8.15 (d, J = 8.0 Hz, 4H, H14), 7.75 (m, 9H, H1 / H4 / H8 / H16), 7.68 (m, 6H, H2 / H13), 7.58 (m, 12H, H3 / H5 / H9 / H12 / H15), 7.12 (m, 8H, H6 / H7 / H10 / H11), 1.50 (s, 9H, H17). 13 13C NMR (100 MHz, DMSO-d6, ppm): δ 154.2, 153.1, 152.7, 151.5, 146.6, 141.6, 141.1, 140.7, 139.6, 139.3, 134.1, 133.6, 131.7, 131.0, 130.8, 127.4, 125.1, 124.7, 124.3, 123.9, 122.9, 122.2, 118.4, 117.4, 78.8, 28.1. ESI-MS m / z, found 1338.9545, calculated for C 71 H 61 N 15 O 12 [M + Na] + 1338.4516。

[0062] Ligand L 2-NH2

[0063] Dissolve 2 g (0.65 g, 0.5 mmol) in 20 mL of dichloromethane, and slowly add trifluoroacetic acid (7 mL) dropwise thereto at room temperature. The reaction solution gradually becomes clear. React for 12 hours. Add saturated NaOH solution to the reaction solution until it becomes neutral. The reaction solution gradually becomes turbid, and yellow solid precipitates. Filter by suction to obtain yellow solid L 2-NH2 (573 mg, 94.3%). 11H NMR (400 MHz, DMSO-d6, ppm): δ 9.92 (s, 2H, Hg), 9.27 (s, 2H, Hf), 8.52 (s, 2H, He), 8.49 (s, 2H, Hd), 8.32 (s, 2H, Hc), 8.15 (m, 6H, Hb / H14), 7.67 (m, 11H, H1 / H2 / H3 / H5 / H8 / H9), 7.55 (m, 10H, H4 / H6 / H7 / H12), 7.11 (m, 8H, H15 / H10 / H11 / H13), 6.68 (d, J = 8.0 Hz, 2H, H16), 5.42 (s, 2H, Ha). 13 13C NMR (100 MHz, DMSO-d6, ppm): δ 154.2, 153.2, 152.7, 148.1, 146.6, 141.9, 140.9, 139.5, 133.8, 131.7, 130.9, 130.7, 128.0, 127.6, 127.3, 125.2, 124.8, 124.4, 124.2, 124.1, 123.9, 122.0, 121.8, 121.7, 118.5, 117.4, 114.5. ESI-MS m / z, found 1238.4321, calculated for C 66 H 53 N 15 O 10 [M + Na] + 1238.3992。

[0064] Ligand L 2-UPy

[0065] L 2-NH2 (50 mg, 0.0411 mmol) was added to 3 mL of tetrahydrofuran and 300 μL of N,N-dimethylformamide in a three-necked flask. H-UPy (15.676 mg, 0.0534 mmol) was dissolved in 500 μL of tetrahydrofuran, and the mixture was refluxed at 85 °C overnight. A solid gradually precipitated, and the solid was collected by filtration to obtain a pale yellow solid L 2-UPy , with a yield of 87.42%. 11H NMR (400 MHz, DMSO-d6, ppm): δ 11.58 (s, 1H, Hk), 9.91 (s, 2H, Hg), 9.67 (s, 1H, Hj), 9.27 (s, 2H, Hf), 8.54 (m, 6H, Hb / Hc / Hd), 8.33 (s, 2H, He), 8.15 (m, 6H, H12 / H14), 7.74 (m, 11H, H1 / H2 / H4 / H8 / H16), 7.68 (m, 14H, H3 / H5 / H9 / H13 / H15), 7.58 (s, 1H, Ha), 7.13 (m, 9H, H6 / H7 / H10 / H11 / H18), 6.16 (s, 1H, Hi), 5.75 (s, 1H, Hh), 3.12 (m, 4H, H19 / H24), 2.13 (s, 3H, H17), 1.44 (m, 4H, H20 / H23), 1.33 (m, 4H, H21 / H22). 13 13C NMR (100 MHz, DMSO-d6, ppm): δ 155.1, 154.6, 154.2, 153.1, 152.7, 151.4, 156.6, 141.1, 140.9, 139.5, 139.1, 138.7, 133.6, 132.7, 132.2, 131.7, 130.8, 130.6, 127.3, 126.9, 125.2, 124.7, 124.4, 124.3, 124.1, 123.9, 122.5, 122.4, 118.4, 117.8, 117.4, 104.4, 30.3, 29.1, 26.0, 23.7. ESI-MS m / z, found 1531.4365, calculated for C 79 H 72 N 20 O 13 [M + Na] + 1531.5479。

[0066] Combining Example 1 and Example 2, Synthesis and Characterization of Complexes

[0067] H 1-NH2 Synthesis and Characterization

[0068] (TBA)3PO4 was prepared by mixing H3PO4 and (TBA)OH in an aqueous solution in a 1:1 ratio. (TBA)3PO4 (2.8 μL, 0.625 mol / L) was added to a 1 mL acetonitrile solution of L 1-NH2 (5 mg, 5.2 μmol). The mixture was stirred at room temperature for ten hours to obtain a clear orange-red solution. The solution was transferred to a glass tube and placed in a large bottle filled with diethyl ether. After slow diffusion for about seven days, bright yellow solid H was obtained1-NH2 (Yield > 85%), scrape it out, drain it, and store it after drying. 1 1H NMR (400 MHz, CD3CN, ppm): δ 13.39 (s, 2H, He), 12.20 (s, 2H, Hd), 11.78 (s, 2H, Hc), 11.56 (s, 2H, Hb), 8.28 (d, J = 8.0 Hz, 2H, H8), 8.10 (d, J = 8.0 Hz, 2H, H5), 7.78 (d, J = 8.0 Hz, 4H, H10), 7.64 (d, J = 8.0 Hz, 4H, H11), 7.58 (d, J = 8.0 Hz, 4H, H9), 7.34 (d, J = 8.0 Hz, 2H, H4), 7.30 (s, 1H, H1), 7.25 (s, 2H, H2), 7.14 (d, J = 8.0 Hz, 4H, H12), 6.97 (m, 4H, H6 / 7), 6.66 (d, J = 8.0 Hz, 2H, H3), 4.18 (s, 2H, Ha), 2.93, 1.45, 1.23 and 0.84 TBA + .

[0069] H 1-UPy Synthesis and Characterization of H

[0070] Prepare (TBA)3PO4 by mixing H3PO4 and (TBA)OH in an aqueous solution in a 1:1 ratio. Add (TBA)3PO4 (3.94 μL, 0.625 mol / L) to a 1 mL acetonitrile solution of L 1-UPy (3 mg, 2.5 μmol). Stir for ten hours at room temperature to obtain a clear reddish-brown solution. Transfer the solution into a glass tube and place it in a large bottle filled with diethyl ether. After slow diffusion for about seven days, an orange-yellow solid H 1-UPy (Yield > 85%) is obtained. Scrape it out, drain it, and store it after drying.

[0071] H 2-NH2 Synthesis and Characterization of H

[0072] Prepare (TBA)3PO4 by mixing H3PO4 and (TBA)OH in an aqueous solution in a 1:1 ratio. Add (TBA)3PO4 (3.94 μL, 0.625 mol / L) to a 1 mL acetonitrile solution of L 2-NH2 (3 mg, 2.5 μmol). Stir for ten hours at room temperature to obtain a clear orange-yellow solution. Transfer the solution into a glass tube and place it in a large bottle filled with diethyl ether. After slow diffusion for about seven days, a bright yellow solid H 2-NH2 (Yield > 85%) is obtained. Scrape it out, drain it, and store it after drying. 11H NMR (400 MHz, CD3CN, ppm): δ 12.82 (s, 2H, Hg), 12.50 (s, 2H, Hf), 12.23 (d, d, J = 8.0 Hz, 2H, He), 11.96 (s, 2H, Hd), 11.92 (s, 2H, Hc), 11.58 (d, J = 8.0 Hz, 2H, Hb), 8.57 (d, J = 8.0 Hz, 2H, H12), 8.49 (m, 2H, H10), 8.03 (m, 2H, H5), 7.94 (d, J = 8.0 Hz, 2H, H8), 7.69 (d, J = 8.0 Hz, 4H, H14), 7.61 (m, H6, H4 / H15), 7.38 (S, 2H, H2), 7.37 (s, 1H, H1), 7.32 (m, 4H, H13), 7.13 (m, 4H, H9 / H11), 6.98 (m, 4H, H6 / H7), 6.89 (m, H6, H3 / H160), 2.91, 1.42, 1.24 and 0.85 TBA + 。

[0073] H 2-UPy Synthesis and Characterization

[0074] H3PO4 and (TBA)OH were prepared into (TBA)3PO4 in an aqueous solution according to a ratio of 1:1. (TBA)3PO4 (5.29 μL, 0.625 mol / L) was added to 1 mL of an acetonitrile solution of L 2-UPy (5 mg, 3.3 μmol). The mixture was stirred at room temperature for ten hours to obtain a clear reddish-brown solution. The solution was filled into a glass tube and placed in a large bottle containing ether. After slow diffusion for about seven days, a pale yellow solid H 2-UPy (yield > 85%) was obtained, scraped out, dried by suction, and stored.

[0075] Combining Example 1 and Example 2, Preparation of Multilevel Self-Assembled Gels

[0076] As Figure 3 , the prepared solid powders of H 1-NH2 , H 1-Upy , H 2-NH2 , H 2-UPy were dissolved in 1 mL of an acetonitrile solution, and the solvent was slowly volatilized to gradually increase the concentration, and finally four supramolecular gels G 1-NH2 (0.232 M), G 1-Upy (0.176 M), G 2-NH2 (0.274 M), G 2-UPy (0.149 M) were obtained.

[0077] As Figure 4 , the prepared H 1-NH2, H 1-Upy , H 2-NH2 , H 2-UPy The solid powders of H 1-NH2 , H 1-Upy , H 2-NH2 , and H 2-UPy were immersed in 1 mL of chloroform solution to obtain four gels G 1-NH2 (Q = 3.86), G 1-Upy (Q = 2.20), G 2-NH2 (Q = 2.82), and G 2-UPy (Q = 2.30) swollen by chloroform.

[0078] Figure 5 It reflects the structures of the ligands (L 1-NH2 , L 1-UPy , L 2-NH2 , L 2-UPy ) and complexes (H 1-NH2 , H 1 , H -UPy , H 2-NH2 , H 2-UPy ) in Examples 1 and 2 of the present invention, as well as the step method of complex gelation.

[0079] Combining Example 1 and Example 2, Rheological Tests of Gels

[0080] As Figure 6 , the prepared complex was dissolved in an acetonitrile solution, and gels were prepared by the method of acetonitrile volatilization at 45 °C. Subsequently, the obtained gels were subjected to rheological tests. The results of frequency scanning in the oscillation mode showed that the storage modulus (G') and loss modulus (G") were almost independent of frequency in a wide range, and G' was always higher than G", indicating the formation of a stable gel. Among them, due to the enhanced hydrogen bond binding ability, the value of the storage modulus G' of the gel formed by the UPy-containing complex was greater than that of the amino-terminated one. The values of the storage modulus and loss modulus of the gel obtained in Example 2 were greater than those of the gel obtained in Example 1 and were more stable.

[0081] Combining Example 1 and Example 2, Scanning Electron Microscope Tests of Gels

[0082] As Figure 7 , SEM samples of the gels formed by acetonitrile volatilization and chloroform swelling were prepared by freeze-drying. The results of scanning electron microscopy (SEM) showed that G 1-NH2 and G 2-NH2 prepared by acetonitrile volatilization presented a three-dimensional network formed by irregular spherical nanoparticles, while G 1-UPy and G 2-UPy were composed of more regular nanospheres; G 1-NH2 and G 2-NH2 prepared by chloroform swelling were in irregular block shapes, and G 1-UPy and G 2-UPy were in more ordered fiber bundle shapes. ​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​

[0083] Combining Example 1 and Example 2, Encapsulation Performance of Gels for Choline

[0084] like Figure 8 After cotton was laid on the bottom of a 1 ml syringe, the complex powder was directly placed in the syringe, and the gel was prepared by the chloroform swelling method and used as a separation column. + The CDCl3 solution was pumped into the gel column at a rate of 100 μL / min by a syringe pump, and the eluate was collected in an NMR tube. 1 H NMR test. As the choline solution is continuously pumped in, the Ch + The signal gradually reaches the initial concentration, and the overall trend is shown in the line graph. + The total load capacity is known, G 2-UPy To Ch + The adsorption capacity of UPy was the highest, which may be due to the well-organized hydrogen bonds between UPy groups, forming a more ordered nanostructure.

[0085] Combining Example 1 and Example 2, Selective Encapsulation and Release Performance of Gels for Choline

[0086] like Figure 9 , H 1-U (20 mg) was directly placed in a 1 mL syringe and swollen with chloroform to obtain G 1-UPy As the stationary phase, a microinjection pump was set to pump Ch into the gel column at a rate of 50 μL / min. + A mixed solution of CDCl3 and DMEA (1.40 mM, 1000 μL) was prepared. Each 500 μL CDCl3 eluate was collected in a NMR tube and 1 H NMR test. The test results show: Ch + The ratio of DMEA changed from 1:1 before pumping to 0:1 after elution, indicating that the gel was + Then, 1500 μL of 1. N 1113 + CDCl3 solution, eluent 1 H NMR spectrum showed Ch + It was successfully released from the gel column. + Before pumping and after release 1 Ch in H NMR + After calculating the integrated area, it can be seen that about 92% of choline was successfully released in the whole process.

[0087] Combining Example 1 and Example 2, Monitoring of Host-Guest Binding in Gels by Electrical Sensing

[0088] like Figure 10 and 11, a conductive syringe with silver electrodes that can be inserted at both ends was prepared. The complex directly swelled into a gel during injection. This device was placed in a Faraday cell and connected to a micro-injection pump and a digital multimeter to form a conductive device system for the electrical testing of the gel. First, the current of the gel under a constant voltage of 1 V was tested through the direct current output by the digital multimeter, and the ionic conductivity of the corresponding gel was calculated according to the formula. The result was G 1-NH2 > G 2-NH2 > G 1 -UPy > G 2-UPy ; Then, the conductivity of the guest molecule solution used in the experiment was tested. The experimental results showed that there were obvious differences in the conductivity of the two guest molecule solutions used in the previous experiment, which laid a theoretical foundation for the real-time monitoring of the whole process of gel encapsulation and release of choline through the change of electrical signals.

[0089] Subsequently, the filtration experiment was repeated with the conductive device system, and the current change during the whole process was as Figure 12 shown in b). During the process of pumping 1000 μL of the CDCl3 solution of the Ch+ and DMEA mixture, the current value increased by about 15%, and the corresponding 1 1H NMR spectrum indicated the encapsulation of Ch+ by the gel column; the current values that gradually increased and the increasing degree gradually decreased after pumping 500 μL of the CDCl3 solution of N 1113 + three times were due to the replacement of Ch + in the gel column by N with stronger conductivity 1113 + , and the corresponding 1 1H NMR spectrum showed the release of Ch + by the gel column.

[0090] Combining Example 1 and Example 2, Recycling Rate of Gels

[0091] As Figure 13 , the gel G 1-UPy (obtained by swelling 100 mg of H 1-UPy with 500 μL of chloroform for 12 h), after a series of recovery operations, finally 81.02 mg of H 1-UPy was obtained again, indicating that the recovery rate of the gel of the present invention can reach more than 80%. First, 100 mg of H 1-UPy was swollen with 500 μL of chloroform for 12 h to obtain the gel G 1-UPy ; then the gel was dissolved by stirring with acetonitrile at 45 °C for 5 h, and then the above solution was poured into deionized water, stirred at room temperature for 5 h, centrifuged and dried to obtain a pale yellow powdery solid L 1-UPy(62.40 mg); Finally, the anionic ligand and (TBA)3PO4 were added to the acetonitrile solution in an equivalent ratio of 3:2, stirred at room temperature for 5 h, then diffused with diethyl ether and dried to obtain 81.02 mg of yellow solid powder H 1-UPy , and the gel G can be obtained after swelling with chloroform 1-UPy . It can be calculated that the recovery rate of the whole process is 81.02%.

[0092] Such as Figure 14 , the gel G obtained in the present invention 2-UPy (86.85 mg of H 1-UPy obtained after swelling with 500 μL of chloroform for 12 h), and finally 66.96 mg of H was obtained again after a series of recovery operations 2-UPy , and the recovery rate was 77.10%. It shows that the recovery and utilization rate of the gel of the present invention can reach more than 80%. First, 86.85 mg of H 2-UPy was swollen with 500 μL of chloroform for 12 h to obtain the gel G 2-UPy ; then acetonitrile was used to stir the gel at 45 °C for 5 h to dissolve it, and then the above solution was poured into deionized water, stirred at room temperature for 5 h, centrifuged and dried to obtain a yellow powdery solid L 2-UPy (50.20 mg); finally, the anionic ligand and (TBA)3PO4 were added to the acetonitrile solution in an equivalent ratio of 2:2, stirred at room temperature for 5 h, then diffused with diethyl ether and dried to obtain 66.96 mg of yellow solid powder H 2 -UPy , and the gel G can be obtained after swelling with chloroform 2-UPy . It can be calculated that the recovery rate of the whole process is 77.10%.

[0093] It can be seen from the above examples that the phosphate anion helical structure complex based on the present invention, in which the supramolecular gel formed by chloroform swelling, provides a new method and idea in the application of host-guest separation in the solid-liquid phase of the stationary phase. The excellent conductivity of the supramolecular gel simultaneously realizes the function of real-time monitoring for the host-guest separation of the gel, and has a high recovery and utilization rate.

Claims

1. A spiral structure, characterized in that, The helical structure is formed by self-assembly of a ligand with triphenylbenzene as the central linker and amino or Upy units at the ends with phosphate anions in an acetonitrile solution.

2. A supramolecular gel, characterized in that, The helical structure described in claim 1 is formed by acetonitrile evaporation or chloroform swelling.

3. The supramolecular gel according to claim 2, wherein The supramolecular gel is prepared by the following preparation method: S3.1 Preparation of the anionic ligand L NH2 : S3.11 Dilute (Boc)2O with tetrahydrofuran, slowly add the diluted solution dropwise to the tetrahydrofuran solution of a, react for twelve hours under an ice bath, sample the reaction solution with silica gel after the reaction is completed, use a eluent of petroleum ether:ethyl acetate = 1:1, separate by silica gel column chromatography, collect the corresponding product solution and rotary evaporate, obtain a pale yellow powdery substance, dry it with an oil pump to obtain compound b; S3.12 Under a nitrogen atmosphere, slowly add the dichloromethane solution of compound b dropwise to the dichloromethane solution of 2-nitroisocyanate, stop the reaction after 4 hours of reaction, and filter to obtain compound c; S3.13 Under an argon-protected environment, hydrazine hydrate diluted with ethanol is added dropwise to the mixture of compound c, Pd / C, and ethanol, react at 85 °C for five hours until the reaction solution turns grayish white, treat the reaction, spread diatomaceous earth on the sintered glass funnel to leave the Pd / C attached with the product on the upper layer of the sintered glass funnel, dissolve the filter cake with N,N-dimethylformamide, filter off the palladium carbon with diatomaceous earth again, rotary evaporate the obtained filtrate and add water to precipitate a white solid d, filter and wash with ether, and dry in vacuo to obtain compound d; S3.14 Dissolve compound d in tetrahydrofuran and N,N-dimethylformamide, after dissolution, dissolve 4-nitrophenyl isocyanate in tetrahydrofuran and add it dropwise to the reaction solution, heat and stir, observe that a yellow product gradually precipitates, react overnight, rotary evaporate the reaction solution, add a poor solvent ether to precipitate a yellow solid, filter, and dry in vacuo to obtain compound e; S3.15 Place compound e in dichloromethane, and slowly add trifluoroacetic acid to it at room temperature. The reaction solution gradually becomes clear. React for twelve hours, add saturated NaOH solution to the reaction solution until it is neutral. The reaction solution gradually becomes turbid, and yellow solid precipitates. Filter by suction to obtain ligand L NH2 ; S3.2 Preparation of Ligand L UPy : Add the ligand L obtained in step S3.15 NH2 to N,N-dimethylformamide. Dissolve H-UPy in tetrahydrofuran, and reflux overnight at 85°C with condensation. Gradually, a solid precipitates. Filter it by suction to obtain a pale yellow solid, which is the ligand L UPy ; S3.3 Preparation of Complex H NH2 : (TBA)3PO4 was prepared by mixing H3PO4 and (TBA)OH in an aqueous solution in a 1:1 ratio. Then, (TBA)3PO4 was added to the ligand L obtained in step S3.1 NH2 in an acetonitrile solution. After stirring at room temperature, a clear solution was obtained. The solution was transferred into a glass tube and placed in a large bottle containing ether. After slow diffusion for about seven days, solid H was obtained NH2 ; S3.4 Preparation of Complex H UPy : Prepare (TBA)3PO4 by mixing H3PO4 and (TBA)OH in an aqueous solution in a 1:1 ratio. Take (TBA)3PO4 and add it to the acetonitrile solution of ligand L UPy obtained in step S3.

2. Stir the solution at room temperature to obtain a clear solution. Transfer the solution into a glass tube and place it in a large bottle filled with ether. After slow diffusion for about seven days, solid H UPy is obtained; S3.5 Acetonitrile evaporation into gel: Dissolve the complex H NH2 or H Upy obtained in step S3.3 or S3.4 in an acetonitrile solution, and slowly evaporate the solvent to gradually increase its concentration, finally obtaining the supramolecular gel G NH2 or G Upy ; S3.6 Swelling into gel with chloroform: Soak the solid powder of the complex H NH2 or H Upy prepared in step S3.3 or S3.4 in a chloroform solution to finally obtain the supramolecular gel G NH2 or G Upy .

4. The supramolecular gel according to claim 3, wherein A further method for optimizing the preparation of the gel is that the compound for performing step S3.15 and subsequent steps is prepared by the preparation methods of steps S3.12 - S3.14 from compound d obtained in step S3.

13.

5. The supramolecular gel according to claim 2 or 3 or 4, characterized in that, The storage modulus value of the gel formed by the UPy complex is greater than that of the amino-terminated one, and the storage modulus value and loss modulus value of the gel obtained by the method of claim 4 are greater than those of the gel obtained by the method of claim 3 and are stable.

6. The supramolecular gel according to claim 2 or 3 or 4, characterized in that, The gel can be used as a stationary phase from choline Ch + and N,N - Selective encapsulation of Ch in a mixed solution of dimethylethanolamine + ; Then, by adding Ch + The competing guest trimethylpropylamine N 1113 + , gel-encapsulated Ch + Can be released to achieve host-guest separation applications in solid-liquid phases.

7. The supramolecular gel according to claim 6, characterized in that, The described host-guest separation application can be monitored in real time by an electrical sensing method.

8. The supramolecular gel according to claim 6, wherein The recovery rate of the gel reaches more than 75%.

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