Preparation method and application of a supramolecular host-guest fluorescence sensing system

Abstract

The invention discloses a method for preparing a supramolecular host-guest fluorescence sensing system, including mixing 4-amino-1,8-naphthalic anhydride, N,N-dimethylethylenediamine and anhydrous ethanol, after the reaction is cooled to room temperature, the reaction is concentrated under reduced pressure and dried to obtain an intermediate product; the intermediate product, benzyl bromide and acetonitrile are mixed, a solid powder is obtained after reflux reaction and dissolved in water, a saturated ammonium hexafluorophosphate solution is added, the precipitation is filtered, and a yellow solid is dried and dissolved in acetonitrile, saturated tetra-n-butylammonium chloride is added, and a yellow precipitate is precipitated, and a GBox-2·A solid is configured with an aqueous solution reserve solution for standby use, while a NI-1·Cl solid is added with deionized water to dissolve, and an aqueous solution reserve solution is configured for standby use, and a mixture of GBox-2·A and NI-1·Cl is prepared according to the host-guest, and a supramolecular host-guest fluorescence sensing system is ultrasonically prepared. The present invention has excellent properties such as accurate structure, stable batch synthesis, and fixed molecular weight, and has the advantages of simple handling, low detection cost, and fast response speed in the detection of polycyclic aromatic hydrocarbons.

Description

Technical Field

[0001] The present invention relates to the field of environmental pollutant sensing and detection control, and in particular to a preparation method and application of a supramolecular host-guest fluorescence sensing system. Background Art

[0002] PAHs are persistent organic pollutants whose chemical structure contains two or more condensed aromatic hydrocarbons. They are mainly formed as a result of pyrolysis processes, especially the incomplete combustion of organic matter in many different activities and industrial processes. Most PAHs are highly lipophilic and have low water solubility, but due to their high mobility, they can be detected in air, water, soil and sediments, usually in the form of complex mixtures. PAHs can be exposed to the environment for a long time and are closely related to human health problems such as DNA damage, immune deficiency, respiratory diseases, etc. Therefore, the detection of PAHs in the environment is very important.

[0003] The supramolecular host-guest fluorescence sensing system can establish the trend relationship between fluorescence intensity and concentration through the fluorescence indicator replacement analysis method. It has the advantages of simple sample processing and fast response speed, and is expected to achieve rapid evaluation of the content of polycyclic aromatic hydrocarbons in the environment. Patent CN114380828B discloses a synthesis method and application of a perylene diimide-based bicyclic compound. The compound has good water solubility and is only used in biomedical fields such as hypoxia-responsive near-infrared photothermal antibacterial and tumor ablation, and has not been applied to the construction of supramolecular host-guest sensing systems and research on environmental monitoring.

[0004] At present, the common methods for determining the content of PAHs are mostly based on chromatography, such as gas chromatography-mass spectrometry and high-performance liquid chromatography. Chromatography is a relatively accurate and highly sensitive detection method, and has a relatively mature determination process for the quantitative detection of PAHs. However, it also has problems such as high price, long cycle, and small detection volume, which makes it difficult to be widely used, greatly limiting the real-time detection of PAHs in the environment. Therefore, it is very necessary to develop a new method that can easily and quickly evaluate the content of PAHs in the environment. Therefore, a preparation method and application of a supramolecular host-guest fluorescence sensing system are needed. Summary of the invention

[0005] The purpose of the present invention is to provide a preparation method and application based on a supramolecular host-guest fluorescence sensing system.

[0006] To achieve the above object, the present invention is implemented according to the following technical solutions:

[0007] The first aspect of the present invention provides a method for preparing a supramolecular host-guest fluorescence sensing system, comprising the following steps:

[0008] The water-soluble macrocyclic main molecule GBox-2·A and NI-1·Cl solid are prepared into aqueous solution, the concentration of the stock solution of GBox-2·A is 1-20μM, and the concentration of the stock solution of NI-1·Cl is 10-40μM;

[0009] The supramolecular host-guest fluorescence sensing system was prepared by mixing the host-guest GBox-2·A and NI-1·Cl in a molar ratio of 0.8-1.2 and then ultrasonically mixing them.

[0010] Furthermore, the ultrasonic time is 10-100 minutes.

[0011] Furthermore, the water-soluble macrocyclic main molecule GBox-2·A is constructed by a conjugated system such as perylene diimide and bipyridyl humide, and its chemical structure is shown in the following formula (I):

[0012]

[0013] In the formula, A is a high hydration energy ion such as a halogen ion, a nitrate ion, a sulfate ion, or a methanesulfonate ion.

[0014] Furthermore, the preparation method of NI-1·Cl comprises the following steps:

[0015] (1) 4-amino-1,8-naphthalene dicarboxylic anhydride, N,N-dimethylethylenediamine and anhydrous ethanol are mixed, and after the heating reaction is completed, the mixture is concentrated under reduced pressure and dried to obtain an intermediate product B;

[0016] (2) mixing the intermediate product B, benzyl bromide and acetonitrile, and subjecting the mixture to reflux reaction to obtain a solid powder,

[0017] (3) dissolving the solid powder in water, adding saturated ammonium hexafluorophosphate solution, filtering the precipitate, and drying to obtain a yellow solid;

[0018] (4) The yellow solid is dissolved in acetonitrile, and saturated tetra-n-butylammonium chloride is added to precipitate a yellow precipitate NI-1·Cl, whose chemical structure is shown in the following formula (II):

[0019]

[0020] Furthermore, in step (1), the molar volume ratio of 4-amino-1,8-naphthalene dicarboxylic anhydride, N,N-dimethylethylenediamine and anhydrous ethanol is 1 mmol: (2.0-6.0) mL: (20-100) mL; the heating temperature is 70-90° C., and the heating time is 2-24 h.

[0021] Furthermore, in step (2), the molar volume ratio of the intermediate product B, benzyl bromide and acetonitrile is 1 mmol: (1.0-6.0) mmol: (20-100) mL; the heating temperature is 70-90° C., and the heating time is 12-48 h.

[0022] Furthermore, the preparation method of the supramolecular host-guest fluorescence sensing system is applied in the evaluation of polycyclic aromatic hydrocarbons content.

[0023] The specific steps include:

[0024] (3) Pipette different concentrations of PAH acetonitrile standard stock solutions, add them into the supramolecular fluorescence sensing system solution, mix and sonicate, and then combine the fluorescence spectrum intensity with the PAH concentration to construct a fluorescence-concentration standard curve.

[0025] (4) The sampling membrane loaded with polycyclic aromatic hydrocarbons is extracted using acetonitrile to obtain a treated polycyclic aromatic hydrocarbon sample.

[0026] (5) mixing the aqueous solution of the supramolecular host-guest fluorescence sensing system obtained according to claim 5 with the PAH sample obtained in step (4) and performing ultrasound to test the fluorescence intensity, and evaluating the PAH content in the actual sample according to the fluorescence-concentration standard curve obtained in step (3).

[0027] Furthermore, the aqueous solution concentration of the supramolecular host-guest fluorescence sensing system (with GBox-2·A as the standard) is 0.1-20 μM, and the ultrasonic time is 10-100 minutes, ensuring the full combination of PAHs and the host molecule GBox-2·A.

[0028] Furthermore, the detection objects are 16 kinds of polycyclic aromatic hydrocarbons in atmospheric particulate matter, including naphthalene, anthracene, phenanthrene, pyrene, acenaphthene, dihydroacenaphthene, fluorene, fluoranthene, benzo[a]anthracene, chrysene, benzo[b]fluoranthene, benzo[k]fluoranthene, benzo[a]pyrene, indeno[1,2,3-cd]pyrene, dibenzo[a,h]anthracene, and benzo[g,h,i]perylene, and the detection result is the total content of the 16 kinds of polycyclic aromatic hydrocarbons.

[0029] Compared with the prior art, the embodiments of the present invention have at least the following advantages or beneficial effects:

[0030] The supramolecular host-guest fluorescence sensing system prepared by the present invention establishes a trend relationship between fluorescence intensity and concentration through a fluorescent indicator replacement analysis method. Compared with traditional chromatography, it has the advantages of simple sample processing, low detection cost, and fast response speed, and is expected to achieve rapid assessment of the content of polycyclic aromatic hydrocarbons in the environment. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] Figure 1It is a schematic diagram of the fluorescence titration spectrum and binding constant fitting curve of GBox-2·4Cl and NI-1·Cl in aqueous solution in the present invention;

[0032] Figure 2 Schematic diagram of the fluorescence titration spectrum and binding constant fitting curve of the supramolecular host-guest fluorescence sensing system NI-1·Cl@GBox-2·4Cl and anthracene in aqueous solution in the present invention;

[0033] Figure 3 Schematic diagram of the fluorescence titration spectrum and binding constant fitting curve of the supramolecular host-guest fluorescence sensing system NI-1·Cl@GBox-2·4Cl and phenanthrene in aqueous solution in the present invention;

[0034] Figure 4 Schematic diagram of the fluorescence titration spectrum and binding constant fitting curve of the supramolecular host-guest fluorescence sensing system NI-1·Cl@GBox-2·4Cl and pyrene in aqueous solution in the present invention;

[0035] Figure 5 It is a schematic diagram of the fluorescence-concentration trend line of the supramolecular host-guest fluorescence sensing system NI-1·Cl@GBox-2·4Cl and 16 kinds of PAHs mixed standard solutions in the present invention;

[0036] Figure 6 This is a fluorescence change diagram after the supramolecular host-guest fluorescence sensing system NI-1·Cl@GBox-2·4Cl in the present invention is mixed with the actual sample. DETAILED DESCRIPTION

[0037] The technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the drawings in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present invention.

[0038] The supramolecular host-guest fluorescence sensing system is constructed by the water-soluble naphthalene imide fluorescent guest molecule NI-1·Cl and the water-soluble macrocyclic host molecule GBox-2·A. The schematic diagram of its structure is as follows:

[0039]

[0040] In this supramolecular host-guest fluorescence sensing system, due to the π-π interaction and hydrophobic interaction between the water-soluble fluorescent guest molecule NI-1·Cl and the water-soluble macrocyclic host molecule GBox-2·A, the fluorescence of NI-1·Cl is significantly quenched, with a lower fluorescence emission intensity; when electron-rich polycyclic aromatic hydrocarbons with a planar conjugated structure are added to the system, due to the stronger π-π interaction and hydrophobic interaction, the polycyclic aromatic hydrocarbons will replace NI-1·Cl, making NI-1·Cl in a free state and restoring good fluorescence properties. Through this fluorescent indicator replacement analysis method, the rapid detection and evaluation of the content of polycyclic aromatic hydrocarbons in the sampling membrane collected from the environment can be achieved.

[0041] Example 1

[0042] A water-soluble naphthalene imide fluorescent indicator molecule, the chemical formula of the compound is C 23 H 24 N3O2Cl, the reaction equation is as follows:

[0043]

[0044] Weigh 4-amino-1,8-naphthalene dicarboxylic anhydride (106.6 mg, 0.5 mmol), add N,N-dimethylethylenediamine (0.109 mL, 1 mmol) and ethanol (50 mL) into a round-bottom flask. Under nitrogen protection, heat at 80°C for 4 h, and concentrate under reduced pressure to obtain solid compound B (127.5 mg, 90%). Compound B: 1 H NMR (600MHz, DMSO-d6, 298K): δ (ppm) = 8.62 (dd, J = 8.4, 1.0Hz, 1H), 8.42 (dd, J = 7.3, 1.0Hz, 1H), 8.18 (d, J = 8.4Hz, 1H ),7.64(dd,J=8.3,7.3Hz,1H),7.46(s,2H),6.84(d,J=8.4Hz,1H),4.11(m,2H),2.47(d,J=6.9Hz,2H),2.20(s,6H). 13 C NMR (101MHz, DMSO-d6, 298K): δ (ppm) = 163.77, 162.86, 152.78, 133.92, 130.97, 129.69 ,129.41,123.88,121.69,119.34,108.14,107.41,56.59,45.26,37.03.HRMS(ESI)m / z calcd for 2:284.14,found:284.1327.

[0045] Weigh compound B (28.3 mg, 0.1 mmol), add benzyl bromide (17.1 mg, 0.1 mmol) and acetonitrile (30 mL) into a round-bottom flask. Under nitrogen protection, heat the reaction at 80 ° C for 24 hours, and concentrate under reduced pressure to obtain a solid powder. The obtained solid is dissolved in deionized water (10 mL), and then a saturated ammonium hexafluorophosphate solution (10 mL) is added. A precipitate is precipitated, filtered, and the precipitate is fully washed with deionized water and dried in a vacuum drying oven to obtain a yellow solid NI-1·PF6 (23.9 mg, 46%). NI-1·PF6: 1 H NMR (600MHz, DMSO-d6, 298K): δ (ppm) = 8.66 (d, J = 9.3Hz, 1H), 8.47 (d, J = 7.3Hz, 1H), 8.23 ​​(d, J = 8.4Hz, 1H), 7.71–7.67 (m, 1H), 7.62 (d, J = 6.4Hz ,2H),7.58(s,2H),7.54(d,J=10.6Hz,2H),7.52(s,1H),6.87(d,J=8.4H z,1H),4.67(s,2H),4.57–4.52(m,2H),3.60–3.55(m,2H),3.11(s,6H). 13 C NMR (101MHz, DMSO-d6, 298K): δ (ppm) = 164.34, 163.21, 153.72, 134.81, 133.53, 131.83, 130.88, 13 0.42,129.44,128.27,124.54,121.92,119.85,108.81,107.45,67.42,49.72,33.64.HRMS(ESI)m / z calcd for[NI-1] + :374.19,found:374.1854.

[0046] Dissolve NI-1·PF6 (15.6 mg, 0.03 mmol) in acetonitrile (10 mL) solution, then add saturated tetra-n-butylammonium chloride (5 mL) to precipitate a yellow precipitate. Wash the precipitate three times with acetonitrile, filter, and dry to obtain a yellow solid NI-1·Cl (11.7 mg, 95%). NI-1·Cl: 1H NMR (600MHz, D2O, 298K): δ (ppm) = 7.76 (d, J = 7.2Hz, 1H), 7.74 (d, J = 8.2Hz, 1H), 7.63 (d, J = 7.5Hz, 2H), 7.60 (d, J = 6.5Hz, 1H), 7.59–7.54 (m ,2H),7.53(d,J=8.3Hz,1H),7.16(t,J=7.7Hz,1H),6.38(d,J=8.3Hz,1H),4.62(s,2H),4.31–4.26(m,2H),3.42–3.38(m,2H),3.21(s,6H).

[0047] Example 2

[0048] Construction of a water-soluble supramolecular host-guest fluorescence sensing system NI-1·Cl@GBox-2·4Cl:

[0049] At 25°C, accurately weigh 1.2 mg (0.82 μmol) of GBox-2·4Cl solid, add deionized water to dissolve, and prepare a 2 μM stock solution for use. Accurately weigh 1.1 mg (2.68 μmol) of NI-1·Cl solid, add deionized water to dissolve, and prepare a 20 μM stock solution for use. Dilute to a 5 μM GBox-2·4Cl aqueous solution and NI-1·Cl aqueous solution for use, prepare a mixture of GBox-2·4Cl and NI-1·Cl in a ratio of 4:5 between the host and guest substances, sonicate at room temperature for 60 minutes, monitor the fluorescence change of NI-1·Cl to ensure the full combination of GBox-2·4Cl and NI-1·Cl, and finally obtain the supramolecular fluorescent sensing system NI-1·Cl@GBox-2·4Cl.

[0050] Example 3

[0051] A method for measuring the binding constants of polycyclic aromatic hydrocarbons via a water-soluble supramolecular host-guest fluorescence sensing system NI-1·Cl@GBox-2·4Cl:

[0052] Add 10 μL of anthracene standard solution of different concentrations to the prepared supramolecular fluorescence sensing system NI-1·Cl@GBox-2·4Cl to prepare a mixture with a total volume of 3 mL. Since the volume ratio of acetonitrile to aqueous solution is very different, it can be regarded as a detection in aqueous solution. Ultrasound was performed at room temperature for 60 minutes. The fluorescence of the displaced indicator NI-1·Cl was detected by fluorescence spectroscopy. The binding constant of the main molecule and the analyte was fitted by nonlinear curve fitting according to the 1:1:1 competitive binding formula, and the corresponding binding constant was obtained. The results are shown in Figure 2 .

[0053] Example 4

[0054] A method for measuring the binding constants of polycyclic aromatic hydrocarbons via a water-soluble supramolecular host-guest fluorescence sensing system NI-1·Cl@GBox-2·4Cl:

[0055] Add 10 μL of phenanthrene standard solution of different concentrations to the prepared supramolecular fluorescence sensing system NI-1·Cl@GBox-2·4Cl to prepare a mixture with a total volume of 3 mL. Since the volume ratio of acetonitrile to aqueous solution is very different, it can be regarded as a detection in aqueous solution. Ultrasound was performed at room temperature for 60 minutes. The fluorescence of the displaced indicator NI-1·Cl was detected by fluorescence spectroscopy. The binding constant of the main molecule and the analyte was fitted by nonlinear curve fitting according to the 1:1:1 competitive binding formula, and the corresponding binding constant was obtained. The results are shown in Figure 3 .

[0056] Example 5

[0057] A method for measuring the binding constants of polycyclic aromatic hydrocarbons via a water-soluble supramolecular host-guest fluorescence sensing system NI-1·Cl@GBox-2·4Cl:

[0058] Add 10 μL of pyrene standard solution of different concentrations to the prepared supramolecular fluorescence sensing system NI-1·Cl@GBox-2·4Cl to prepare a mixture with a total volume of 3 mL. Since the volume ratio of acetonitrile to aqueous solution is very different, it can be regarded as a detection in aqueous solution. Ultrasonication was performed at room temperature for 60 minutes. The fluorescence of the displaced indicator NI-1·Cl was detected by fluorescence spectroscopy. The binding constant of the main molecule and the analyte was fitted by nonlinear curve fitting according to the 1:1:1 competitive binding formula, and the corresponding binding constant was obtained. The results are shown in Figure 4 .

[0059] Example 6

[0060] A method for evaluating the content of polycyclic aromatic hydrocarbons in real samples by using a water-soluble supramolecular host-guest fluorescence sensing system NI-1·Cl@GBox-2·4Cl:

[0061] Pipette 50 μL of the prepared 16 PAH stock solutions in acetonitrile, and then add the prepared supramolecular fluorescence sensing system NI-1·Cl@GBox-2·4Cl to prepare a mixture with a total volume of 3 mL. Since the volume ratio of acetonitrile to aqueous solution is very different, it can be regarded as a detection in aqueous solution. Ultrasonication was performed at room temperature for 60 minutes, and the fluorescence of the displaced indicator NI-1·Cl was detected by fluorescence spectroscopy. Combined with the concentration of PAHs, a fluorescence-concentration standard curve can be constructed (see the results). Figure 5 ).

[0062] The atmospheric particulate sampling membrane loaded with PAHs was extracted with acetonitrile, and the PAH sample was obtained after removing the acetonitrile by rotary evaporation. Subsequently, 50 μL of acetonitrile was added to the PAH solid in the actual sample to dissolve it, and then the prepared supramolecular fluorescence sensing system NI-1·Cl@GBox-2·4Cl aqueous solution was added to prepare a mixture with a total volume of 3 mL. Since the volume ratio of acetonitrile to aqueous solution is very different, it can be regarded as a detection in aqueous solution. Ultrasonication was performed at room temperature for 60 minutes. The fluorescence of the free indicator molecule NI-1·Cl was detected by fluorescence spectroscopy. The content of PAHs in the actual sample was evaluated by constructing a fluorescence-concentration standard curve. Different actual samples were tested under the same experimental conditions, and different fluorescence recovery values ​​were observed, such as Figure 6 By comparing and analyzing the fluorescence-concentration standard curve, the total content of PAHs in the actual sample can be obtained, which is consistent with the content data determined by gas chromatography-mass spectrometry, as shown in Table 1.

[0063] Table 1 PAH content in actual samples of single-piece sampling membrane

[0064]

[0065] The above contents are merely examples and explanations of the structure of the present invention. The technicians in this technical field may make various modifications or additions to the specific embodiments described or replace them in a similar manner. As long as they do not deviate from the structure of the invention or exceed the scope defined by the claims, they should all fall within the protection scope of the present invention.

Claims

1. A method for preparing a supramolecular host-guest fluorescence sensing system, characterized in that: The steps include: The water-soluble macrocyclic main molecule GBox-2·4A and NI-1·Cl solid are prepared into aqueous solution, the concentration of the stock solution of GBox-2·4A is 1-20μM, and the concentration of the stock solution of NI-1·Cl is 10-40μM; The supramolecular host-guest fluorescence sensing system was prepared by mixing the host-guest GBox-2·4A and NI-1·Cl in a molar ratio of 0.8-1.2 and then ultrasonically mixing them. The water-soluble macrocyclic main molecule GBox-2·4A is constructed by a perylene diimide group and a bipyridyl uranium salt conjugated system, and its chemical structure is shown in the following formula (I): Wherein A is a high hydration energy ion such as a halogen ion, a nitrate ion, a sulfate ion, or a methanesulfonate ion; The preparation method of the NI-1·Cl comprises the following steps: (1) 4-amino-1,8-naphthalene dicarboxylic anhydride, N,N-dimethylethylenediamine and anhydrous ethanol are mixed, and after the heating reaction is completed, the mixture is concentrated under reduced pressure and dried to obtain an intermediate product B; (2) mixing the intermediate product B, benzyl bromide and acetonitrile, and subjecting the mixture to reflux reaction to obtain a solid powder, (3) dissolving the solid powder in water, adding saturated ammonium hexafluorophosphate solution, filtering the precipitate, and drying to obtain a yellow solid; (4) The yellow solid is dissolved in acetonitrile, and saturated tetra-n-butylammonium chloride is added to precipitate a yellow precipitate NI-1·Cl, whose chemical structure is shown in the following formula (II):

2. The method for preparing a supramolecular host-guest fluorescence sensing system according to claim 1, characterized in that: The ultrasonic time is 10-100 minutes.

3. The method for preparing a supramolecular host-guest fluorescence sensing system according to claim 1, characterized in that: In step (1), the molar volume ratio of 4-amino-1,8-naphthalene dicarboxylic anhydride, N,N-dimethylethylenediamine and anhydrous ethanol is 1 mmol: (2.0-6.0) mL: (20-100) mL; the heating temperature is 70-90° C., and the heating time is 2-24 h.

4. The method for preparing a supramolecular host-guest fluorescence sensing system according to claim 1, characterized in that: In step (2), the molar volume ratio of the intermediate product B, benzyl bromide and acetonitrile is 1 mmol: (1.0-6.0) mmol: (20-100) mL; the heating temperature is 70-90° C., and the heating time is 12-48 h.

5. Application of the preparation method of a supramolecular host-guest fluorescence sensing system according to claims 1-4 in the evaluation of polycyclic aromatic hydrocarbons content.

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