Mispaired decameric cucurbituril-based assemblies and their application for detection and removal of trinitrophenol

Abstract

The application discloses a misaligned ten-membered cucurbituril-based assembly and application thereof in detecting and removing trinitrophenol. The assembly is assembled by using misaligned ten-membered cucurbituril and 8-hydroxyquinoline as raw materials. The misaligned ten-membered cucurbituril-based assembly is a novel supramolecular assembly, can be used for fluorescent identification of trinitrophenol in an aqueous solution, and has the characteristics of simple detection instrument, high selectivity, good sensitivity, wide detection range, fast response time, and the like. In addition, the misaligned ten-membered cucurbituril-based assembly has the characteristic of being capable of removing trinitrophenol in the aqueous solution.

Description

TECHNICAL FIELD

[0001] The present application relates to a supramolecular assembly and its application, in particular, a misaligned ten-membered cucurbituril-based assembly and its application in detecting and removing trinitrophenol. BACKGROUND

[0002] Nitroaromatic compound 2,4,6-trinitrophenol (TNP), commonly known as picric acid, is not only a dangerous component of explosives, but also a pollutant in water and soil, which can cause dangerous damage to internal organs and nervous system.

[0003] Effective recognition and removal of TNP in the environment is very attractive and important to scientists.

[0004] Currently, the methods for recognizing and detecting trinitrophenol in the environment mainly include colorimetric immunoassay, surface-enhanced Raman spectroscopy and ion mobility spectrometry, etc. Although these detection methods have good selectivity and accuracy, they also have the defects of high operation cost, portability during on-site use and the need for frequent calibration. In contrast, fluorescence method is considered to be an ideal method for environmental monitoring and biological research due to its simple detection instrument, high selectivity, good sensitivity, wide detection range, fast response time and minimal damage to samples.

[0005] Therefore, it is necessary to develop a high-efficiency, rapid and low-cost fluorescence-enhanced organic framework material for detecting TNP in the environment. SUMMARY

[0006] The purpose of the present application is to provide a misaligned ten-membered cucurbituril-based assembly and its application in detecting and removing trinitrophenol. The misaligned ten-membered cucurbituril-based assembly of the present application is a new type of supramolecular assembly, which can be used for fluorescent recognition of trinitrophenol in aqueous solution, has the characteristics of simple detection instrument, high selectivity, good sensitivity, wide detection range and fast response time, and in addition, the misaligned ten-membered cucurbituril-based assembly of the present application also has the characteristics of being able to remove trinitrophenol in aqueous solution.

[0007] The technical solution of the present application is a misaligned ten-membered cucurbituril-based assembly, the molecular formula of which is C 76 H 86 Cd2Cl 10 N 42 O 26 , and the molecular configuration is as shown below:

[0008]

[0009] Among them, is a misaligned ten-membered cucurbituril, is 8-hydroxyquinoline.

[0010] The aforementioned dislocation ten-membered cucurbituril-based assembly is assembled by using dislocation ten-membered cucurbituril and 8-hydroxyquinoline as raw materials.

[0011] The aforementioned dislocation ten-membered cucurbituril-based assembly is assembled by using dislocation ten-membered cucurbituril and 8-hydroxyquinoline as raw materials.

[0012] a. Take 8-hydroxyquinoline, dislocation ten-membered cucurbituril and inducer CdCl2, mix and dissolve with hydrochloric acid to obtain solution A;

[0013] b. Transfer solution A to an autoclave lined with polytetrafluoroethylene, and keep the temperature at 140-160°C for 2-4 hours, then cool it to room temperature, and transfer it to a beaker, and stand at room temperature until crystal B is obtained;

[0014] c. Filter and collect crystal B, which is the dislocation ten-membered cucurbituril-based assembly, which detects and removes 3-nitrophenol in aqueous solution, 1 HNMR spectrum as Figure 6 shown.

[0015] The aforementioned dislocation ten-membered cucurbituril-based assembly, in step a, the molar ratio of 8-hydroxyquinoline to dislocation ten-membered cucurbituril is 2:1, and the mass ratio of 8-hydroxyquinoline to CdCl2 is 5:4. Its molecular weight is 2579.13, and its action ratio is determined by ultraviolet-visible absorption spectrum as Figure 5 .

[0016] The aforementioned dislocation ten-membered cucurbituril-based assembly, in step a, the molar concentration of hydrochloric acid is 6 mol / L.

[0017] The aforementioned dislocation ten-membered cucurbituril-based assembly in the application of detecting 3-nitrophenol in aqueous solution.

[0018] The aforementioned dislocation ten-membered cucurbituril-based assembly in the application of detecting 3-nitrophenol in aqueous solution, the detection method is as follows:

[0019] a. Take the aforementioned dislocation ten-membered cucurbituril-based assembly, dissolve it in water, and prepare a standard solution with a concentration of 2×10 -5 mol / L;

[0020] b. Add the aqueous solution to be tested to the standard solution. If the fluorescence intensity of the solution increases and a precipitate appears, it indicates that the aqueous solution to be tested contains 3-nitrophenol, otherwise it does not.

[0021] The aforementioned dislocation ten-membered cucurbituril-based assembly in the application of removing 3-nitrophenol in aqueous solution.

[0022] The aforementioned dislocation ten-membered cucurbituril-based assembly in the application of removing 3-nitrophenol in aqueous solution, the removal method is as follows:

[0023] a. The dislocation ten-membered cucurbituril-based assembly is dissolved in water to obtain a solution;

[0024] b. The solution of step a is added with an aqueous solution containing trinitrophenol, and after stirring uniformly, it is left to stand until no more precipitate is produced, and then the trinitrophenol in the aqueous solution can be removed by filtration.

[0025] Advantages of the present application

[0026] 1. The dislocation ten-membered cucurbituril-based assembly of the present application is a novel assembly compound formed by dislocation ten-membered cucurbituril and 8-hydroxyquinoline.

[0027] 2. The dislocation ten-membered cucurbituril-based assembly of the present application can be used for identifying trinitrophenol in an aqueous solution by fluorescence method, and has the advantages of simple detection instrument, high selectivity, good sensitivity, wide detection range, and fast response time.

[0028] 3. The dislocation ten-membered cucurbituril-based assembly of the present application can also be used for removing trinitrophenol in an aqueous solution, and further expands the application range on the basis of the application of identifying trinitrophenol in an aqueous solution. BRIEF DESCRIPTION OF DRAWINGS

[0029] Figure 1 is a two-dimensional network diagram of the supramolecular assembly of the present application; (a) top view; (b) front view;

[0030] Figure 2 is the intermolecular hydrogen bond between the dislocation ten-membered cucurbituril molecule and the 8-hydroxyquinoline molecule in the assembly of the present application;

[0031] Figure 3 is that two 8-hydroxyquinoline molecules are included in the dislocation ten-membered cucurbituril host to form a near coplanar structure in the assembly of the present application;

[0032] Figure 4 is the spatial arrangement structure of the dislocation ten-membered cucurbituril and the two 8-hydroxyquinoline molecules in the vertical direction in the assembly of the present application;

[0033] Figure 5 (a) UV-Vis spectrum of 8-hydroxyquinoline after adding dislocation ten-membered cucurbituril in an aqueous solution at 298K (8-hydroxyquinoline = 2.0×10 -5 M, and dislocation ten-membered cucurbituril = 0-2.0×10 -5 M); (b) UV-Vis spectrum fitting diagram of dislocation ten-membered cucurbituril / 8-hydroxyquinoline;

[0034] Figure 6 is the dislocation ten-membered cucurbituril (1.0×10 -41H NMR spectrum (400 MHz, D2O, 298 K) of the assembly of M);

[0035] Figure 7 (a) The fluorescence spectra of the assembly of the present application (2.0 x 10 -5 M) with the gradual addition of TNP; (b) The fitting plot of the change of fluorescence intensity with the change of N [TNP] / N [8-HQ@ns-Q

[10] ] ; (c) The fluorescence response of the assembly of the present application to some phenols (HQ, 2,4-DCP, mAP, PE, 4-IP); (d) The photos of the assembly of the present application with the dropwise addition of HQ, 2,4-DCP, mAP, PE, 4-IP and TNP from left to right, respectively;

[0036] Figure 8 The linear fitting curve of the change of fluorescence intensity of the assembly of the present application with different concentrations of TNP (λem= 496 nm) and different concentrations of TNP;

[0037] Figure 9 (a) The standard curve of the UV absorption of TNP; (b) The square plot of the absorption efficiency of the assembly of the present application to different concentrations (0-100 μM) of TNP; (c) The UV absorption spectra (before and after adsorption) of 100 μM TNP;

[0038] Figure 108 - The fluorescence spectra of HQ@ns-Q

[10] -TNP (2.0 x 10 -5 mol / L) in the presence of 10 eq of other phenolic pollutants, respectively. DETAILED DESCRIPTION

[0039] The present application will be further described in conjunction with the following examples, but it is not intended to be limited by the examples.

[0040] Embodiments of the present application

[0041] Example 1

[0042] A misaligned ten-membered cucurbituril-based assembly is prepared by the following method:

[0043] a. Take 8-hydroxyquinoline (100 mg, 0.208 mmol), misaligned ten-membered cucurbituril (450 mg, 0.604 mmol) and CdCl2(40 mg, 2.1 mmol), mix and then dissolve in hydrochloric acid (6 mol / L, 10 ml) to obtain solution A;

[0044] b. Transfer solution A to a high-pressure kettle lined with polytetrafluoroethylene, and keep the temperature at 150°C for 3 hours, then cool it to room temperature, and transfer it to a beaker, and let it stand at room temperature to obtain crystal B;

[0045] c. Filter and collect crystal B, which is a dislocated ten-membered cucurbit ring-based assembly. The two-dimensional network and structural arrangement of the crystal are as follows: Figures 1-4 shown.

[0046] Example 2

[0047] A dislocated ten-membered cucurbit ring-based assembly is prepared by the following method:

[0048] a. Take 8-hydroxyquinoline (100 mg, 0.208 mmol), misaligned ten-membered cucurbitacin (450 mg, 0.604 mmol) and CdCl2 (40 mg, 2.1 mmol), mix and dissolve in hydrochloric acid (6 mol / L, 10 ml) to obtain solution A;

[0049] b. Solution A was transferred to a polytetrafluoroethylene-lined autoclave and kept at 140°C for 4 hours, then cooled to room temperature and transferred to a beaker and allowed to stand at room temperature until crystals B were obtained;

[0050] c. Filter and collect crystal B, which is the dislocated ten-membered cucurbitacin assembly.

[0051] Example 3

[0052] A dislocated ten-membered cucurbit ring-based assembly is prepared by the following method:

[0053] a. Take 8-hydroxyquinoline (100 mg, 0.208 mmol), misaligned ten-membered cucurbitacin (450 mg, 0.604 mmol) and CdCl2 (40 mg, 2.1 mmol), mix and dissolve in hydrochloric acid (6 mol / L, 10 ml) to obtain solution A;

[0054] b. Solution A was transferred to a polytetrafluoroethylene-lined autoclave and kept at 160°C for 2 hours, then cooled to room temperature and transferred to a beaker and allowed to stand at room temperature until crystals B were obtained;

[0055] c. Filter and collect crystal B, which is the dislocated ten-membered cucurbitacin assembly.

[0056] Example 4

[0057] Application of a misaligned ten-membered cucurbitacin assembly in detecting trinitrophenol in aqueous solution, the method is as follows:

[0058] a. Take the dislocated ten-membered cucurbit ring base assembly, dissolve it in water, and configure it to a concentration of 2×10 -5 mol / L standard solution;

[0059] b. Add the test aqueous solution to the standard solution. If the fluorescence intensity of the solution increases and a precipitate appears, it indicates that the test aqueous solution contains trinitrophenol. Otherwise, it does not contain trinitrophenol.

[0060] c. Qualitative test process: add the standard solution (volume 3mL and concentration 2×10 -5 When different phenol solutions (hydroquinone (HQ), 2,4-dichlorophenol (2,4-DCP), m-aminophenol (mAP), phenol (Pe), 1-(imidazolyl)phenol (4-IP), trinitrophenol (TNP)) were added to 100 mol / L of 4% paraformaldehyde (Pb) solution, only trinitrophenol led to an increase in the fluorescence intensity of the system and the occurrence of precipitation, while the other phenols did not affect the fluorescence of the system and no precipitation occurred. The results are shown in Figure 2. Figure 7 (c) (d)

[0061] d. Quantitative test process: add the standard solution (volume 3mL, concentration 2×10 -5 Fluorescence spectrum detection was performed on solutions of trinitrophenol with different amounts of the substance added to 10 mol / L. As the concentration of trinitrophenol continued to increase, the fluorescence intensity of the supramolecular assembly system continued to rise at 496 nm until the concentration of trinitrophenol reached 20 times the concentration of the supramolecular assembly, at which time a visible precipitation appeared and the change in fluorescence intensity reached equilibrium, as shown in FIG. Figure 7 (a)(b) and Figure 8 As shown, the detection limit is 2.07×10 -5 mol / L.

[0062] Example 5

[0063] Application of a misaligned ten-membered cucurbitacin assembly in removing trinitrophenol from an aqueous solution, the method is as follows:

[0064] a. Take the dislocated ten-membered cucurbit ring-based assembly and dissolve it in water to obtain a solution;

[0065] b. Add an aqueous solution containing trinitrophenol to the solution in step a, stir evenly and let stand until precipitation no longer occurs, and then filter to remove trinitrophenol from the aqueous solution.

[0066] Experimental Example 1

[0067] 1) First prepare different concentrations of TNP (1.0×10 -5 M,2.0×10 -5 M···9,1.0×10 -4 M), test their absorbance respectively, and plot the absorbance against concentration ( Figure 9(b)), the linearity of the fitting indicates that the absorbance of TNP is consistent with the Lambert-Beer law in this concentration range, and the absorbance is linearly corresponding to the concentration. In the following experiments, the concentration of TNP can be converted from the absorbance according to this working curve.

[0068] 2) To the TNP solutions with different concentrations (1.0×10-5M, 2.0×10-5M···, 1.0×10-4M) in step 1), the assembly solution (2×10 -5 M) of the present application was added respectively. After stirring for 1 hour at room temperature in the dark, the absorbance of each solution was measured by UV-Vis spectrophotometer. Figure 9 (a) (c) shows that the removal rate is greater than 89%.

[0069] Experimental Example 2

[0070] Phenolic solutions were prepared, and the phenolic solutions respectively included: hydroquinone (HQ), 2,4-dichlorophenol (2,4-DCP), m-aminophenol (mAP), phenol (Pe), 1-(imidazolyl) phenol (4-IP). The molar concentration of the phenolic solution was 0.2 mol / L.

[0071] Five standard solutions of the assembly of the present application were prepared (volume of 3 mL, concentration of 2×10 -5 mol / L), 20 times of TNP solution was added to the system to make the detection of TNP by the supramolecular assembly system reach the saturation state, and then 5 kinds of phenolic solutions, hydroquinone (HQ), 2,4-dichlorophenol (2,4-DCP), m-aminophenol (mAP), phenol (Pe), 1-(imidazolyl) phenol (4-IP) were added to the system respectively. When sufficient TNP was added to the supramolecular assembly system, the fluorescence increased significantly, and the fluorescence of the system did not change when the 5 kinds of phenolic solutions were continuously added, as shown in Figure 10 , which proves that other phenols will not interfere with the detection of TNP by the system.

[0072] The above is only a preferred embodiment of the present application, but the protection scope of the present application is not limited thereto. Any skilled person in the art can make equivalent replacements or changes to the technical solutions and inventive concepts of the present application within the technical scope disclosed by the present application, which should be covered within the protection scope of the present application.

Claims

1. An application of a misplaced ten-membered cucurbitacin assembly in detecting trinitrophenol in an aqueous solution, characterized in that: The molecular formula of the assembly is C 76 H 86 Cd2Cl 10 N 42 O 26 , the molecular configuration is shown below: The specific preparation method of the assembly is as follows: a. Take 8-hydroxyquinoline, dislocated ten-membered cucurbitacin and CdCl2, mix and dissolve in hydrochloric acid to obtain solution A; b. Solution A was transferred to a polytetrafluoroethylene-lined autoclave and kept at a constant temperature of 140-160°C for 2-4 hours, then cooled to room temperature and transferred to a beaker and allowed to stand at room temperature until crystals B were obtained; c. Filter and collect crystal B, which is the dislocated ten-membered cucurbitacin assembly.

2. The use of the dislocated ten-membered cucurbitacin assembly according to claim 1 in detecting trinitrophenol in an aqueous solution, characterized in that: In the step a, the molar ratio of 8-hydroxyquinoline to the misaligned ten-membered cucurbitacin is 2:1, and the mass ratio of 8-hydroxyquinoline to CdCl2 is 5:

4.

3. The use of the misplaced ten-membered cucurbitacin assembly according to claim 1 in detecting trinitrophenol in an aqueous solution, characterized in that: In the step a, the molar concentration of hydrochloric acid is 6 mol / L.

4. The use of the misplaced ten-membered cucurbitacin assembly according to claim 1 in detecting trinitrophenol in an aqueous solution, wherein The detection method is as follows: a. Take the dislocated ten-membered cucurbit ring-based assembly, dissolve it in water, and configure it to a concentration of 2×10 -5 mol / L standard solution; b. Add the aqueous solution to be tested to the standard solution. If the fluorescence intensity of the solution increases and a precipitate appears, it means that the aqueous solution to be tested contains trinitrophenol; otherwise, it does not.

5. Use of the misplaced ten-membered cucurbitacin assembly according to claim 1 in removing trinitrophenol from an aqueous solution.

6. The use of the misplaced ten-membered cucurbitacin assembly according to claim 5 in removing trinitrophenol in an aqueous solution, characterized in that The removal method is as follows: a. Take the dislocated ten-membered cucurbit ring-based assembly, dissolve it in water to obtain a solution; b. Add an aqueous solution containing trinitrophenol to the solution in step a, stir evenly and let stand until precipitation no longer occurs, and then filter to remove trinitrophenol from the aqueous solution.

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