A hydrazinonaphthalimide functionalized pillar[5]arene, supramolecular assembly, thin film sensor and preparation method and application thereof

Abstract

The present application belongs to the technical field of formaldehyde detection, and particularly relates to a hydrazinyl naphthalimide functionalized pillar[5]arene, a supramolecular assembly, a thin film sensor and a preparation method and application thereof. The hydrazinyl naphthalimide functionalized pillar[5]arene provided by the present application takes a pillar[5]arene with a specific cavity as a skeleton, and hydrazinyl naphthalimide is used as a fluorescent detection group, which can detect formaldehyde and recognize specific guest molecules to form a supramolecular assembly. The supramolecular assembly provided by the present application has good stability in liquid and solid modes, has a low detection limit, a short response time and is convenient to use, and can be used to make a thin film sensor which is convenient to carry and use. The thin film sensor can be used for gaseous formaldehyde detection and recognition.

Description

Technical Field

[0001] The present invention belongs to the technical field of formaldehyde detection, and specifically relates to a hydrazine-naphthalene imide functionalized column [5] aromatic hydrocarbon, a supramolecular assembly, a thin film sensor, and a preparation method and application thereof. Background Art

[0002] Formaldehyde is a colorless, volatile gas with a pungent odor. Short-term exposure can cause discomfort such as red eyes, sore throat, sneezing, and chest tightness. Long-term inhalation can lead to poisoning or even death. As a key chemical raw material, formaldehyde comes from a wide range of sources, including combustion, various coatings, and adhesives. In recent years, the use of inferior decoration materials and the overuse of preservatives have led to excessive levels of formaldehyde in indoor air. In 2004, the International Agency for Research on Cancer (IARC) designated formaldehyde a carcinogen.

[0003] Formaldehyde has posed a serious threat to human health and the ecological environment, and currently reported formaldehyde detection methods have certain limitations. Therefore, the development of a simple, sensitive, and efficient formaldehyde detection method or product is of great significance. Summary of the Invention

[0004] In response to the above technical problems, the present invention provides a hydrazine-naphthalene imide functionalized column [5] aromatic hydrocarbon, a supramolecular assembly, a thin film sensor, and a preparation method and application thereof. The hydrazine-naphthalene imide functionalized column [5] aromatic hydrocarbon provided by the present invention can specifically identify and detect formaldehyde, and can recognize specific guest molecules to form a supramolecular assembly. Through the supramolecular self-assembly strategy, it solves the problems of high formaldehyde detection limit, long response time, and portability problems existing in existing detection methods.

[0005] In order to achieve the above-mentioned object of the invention, the present invention adopts the following technical solutions:

[0006] The first aspect of the present invention provides a hydrazine-naphthalimide functionalized pillar [5] arene, the structural formula of which is shown in Formula I:

[0007]

[0008] Formula I.

[0009] The hydrazine-naphthalene imide functionalized pillar [5] arene provided by the present invention has a pillar [5] arene with a specific cavity as the skeleton, and hydrazine-naphthalene imide as the fluorescent detection group. Experiments have shown that the supramolecular assembly constructed by the hydrazine-naphthalene imide functionalized pillar [5] arene has a certain stability in air and is insensitive to both air and light; it has specific recognition only for formaldehyde and has no response to other aldehydes, laying the foundation for the subsequent preparation of detection sensors based on supramolecular assemblies. Based on the above characteristics, the hydrazine-naphthalene imide functionalized pillar [5] arene as the main body can not only detect formaldehyde, but also recognize specific guest molecules to form supramolecular assemblies.

[0010] The second aspect of the present invention provides a method for preparing the above-mentioned hydrazine-naphthalimide functionalized pillar [5] aromatic hydrocarbon, which specifically comprises the following steps:

[0011] S1. Dissolve column [5] aromatic hydrocarbon and sodium azide in a mixture of N,N-dimethylformamide and water, react at 60-80°C for 2-3 hours, then add sodium sulfide nonahydrate aqueous solution, continue to react for 3-5 hours, cool to room temperature, put the reaction solution into water, separate the solid and liquid, and obtain a white solid;

[0012] S2. React the white solid obtained in S1, 4-bromo-1,8-naphthalene dicarboxylic anhydride and anhydrous ethanol at 60-90°C for 13-15 hours, cool, separate the solid and the liquid, and purify the obtained solid by column chromatography with an eluent of dichloromethane:methanol = 500:1. Collect the eluted fractions and remove the solvent to obtain a yellow solid.

[0013] S3. Dissolve the yellow solid obtained in S2 in hydrazine hydrate, heat to 120-140° C., react for 3-4 hours, cool, separate the solid and the liquid, and obtain the crude solid phase of the hydrazine-naphthaleneimide functionalized column [5] aromatic hydrocarbon.

[0014] The reaction process of this preparation method is as follows:

[0015]

[0016] This preparation method prepares hydrazine-naphthalimide functionalized pillar[5]arene through a concise synthetic route. The synthetic steps are simple, the reaction is efficient, and it is suitable for large-scale synthesis.

[0017] In combination with the second aspect, the molar ratio of the pillar [5] aromatic hydrocarbon, sodium azide, and sodium sulfide nonahydrate in S1 is 1:(4-8):(8-9), preferably 1:6:9.

[0018] Preferably, the mass volume ratio of the column [5] aromatic hydrocarbon to N,N-dimethylformamide in S1 is 1:(20-30) (g:ml); the mass volume ratio of the column [5] aromatic hydrocarbon to water is 1:(2-3) (g:ml).

[0019] Preferably, the concentration of the sodium sulfide nonahydrate aqueous solution in S1 is 1 mM to 2.5 mM.

[0020] In combination with the second aspect, the reaction conditions of column [5]arene and sodium azide in N,N-dimethylformamide and water in S1 are preferably a reaction temperature of 80° C. and a reaction time of 3 hours.

[0021] In combination with the second aspect, the reaction time after adding the sodium sulfide nonahydrate aqueous solution in S1 is preferably 4 hours.

[0022] In combination with the second aspect, the molar ratio of the pillar[5]arene described in S1 to the 4-bromo-1,8-naphthalene dicarboxylic anhydride described in S2 is 1:(3-4), preferably 1:3.

[0023] In combination with the second aspect, the reaction conditions of the white solid and 4-bromo-1,8-naphthalene dicarboxylic anhydride in anhydrous ethanol in S2 are preferably a reaction temperature of 80° C. and a reaction time of 14 hours.

[0024] In combination with the second aspect, the molar ratio of the pillar [5] aromatic hydrocarbon in S1 to the hydrazine hydrate in S3 is 1:(1000-2000), preferably 1:2000.

[0025] In combination with the second aspect, S3 further comprises purifying the crude product of the hydrazine-naphthalimide functionalized column [5] aromatic hydrocarbon by recrystallizing the obtained solid phase in n-hexane.

[0026] In combination with the second aspect, after the yellow solid is dissolved in hydrazine hydrate in S3, the mixture is preferably heated to 130° C. and reacted for 3 hours.

[0027] The third aspect of the present invention provides a supramolecular assembly, which is made of the above-mentioned hydrazine-naphthalimide functionalized pillar [5] aromatic hydrocarbon and a high molecular polymer.

[0028] In conjunction with the third aspect, the structural formula of the high molecular polymer is shown in Formula II:

[0029]

[0030] Formula II.

[0031] The polymer is a polymer chain formed by combining methyl methacrylate and 5-bromopentanenitrile. 5-bromopentanenitrile can be recognized as a guest unit by pillar[5]arene, and the resulting supramolecular assembly can be made into a device; and polymethyl methacrylate has good mechanical properties, so that the supramolecular assembly can be used to make a thin film sensor.

[0032] The supramolecular assembly made of the hydrazinyl naphthalimide functionalized pillar[5]arene and the polymer has good stability in liquid and solid modes, low detection limit, short response time, and is easy to use, and can be used to make a thin film sensor which is convenient to carry and use, and has important significance for the super-sensitive and convenient detection of formaldehyde.

[0033] Preferably, the preparation method of the polymer specifically comprises the following steps:

[0034] Step a, 4-hydroxystyrene, 5-bromopentanenitrile, anhydrous potassium carbonate, potassium iodide are dissolved in acetonitrile, refluxed at 60-80℃ for 30-40 hours under inert atmosphere, cooled, solid-liquid separation, collect the liquid phase, purify the liquid phase by column chromatography, the eluent is pure dichloromethane, collect the elution fraction, remove the solvent, and get yellow oily liquid;

[0035] Step b, mix the yellow oily liquid obtained in step a with methyl methacrylate, 2-(dodecyltrithiocarbonate)-2-methylpropionic acid, azobisisobutyronitrile in anhydrous tetrahydrofuran, heat to 70-90℃, react for 50-65 hours, cool, pour the reaction liquid into n-hexane, solid-liquid separation, collect the solid phase, and get the crude product of the polymer.

[0036] The reaction process of the preparation method is as follows:

[0037]

[0038] The above preparation method synthesizes a polymethyl methacrylate polymer chain containing 5-bromopentanenitrile through raft polymerization reaction, which has mild reaction conditions and high yield, and can be used for industrial production.

[0039] Preferably, the molar ratio of 4-hydroxystyrene, 5-bromopentanenitrile, anhydrous potassium carbonate, potassium iodide in step a is 1:(1-1.5):(4-6):(0.15-0.20). Further preferably, the molar ratio is 1:1:4:0.15.

[0040] Preferably, the reflux temperature in step a is 60℃, and the time is 36 hours.

[0041] Preferably, the molar ratio of 4-hydroxystyrene in step a to methyl methacrylate, 2-(dodecyltrithiocarbonate)-2-methylpropionic acid, and azobisisobutyronitrile in step b is 1:(6-9):(0.002-0.004):(0.002-0.005). A further preferred molar ratio is 1:8:0.003:0.003.

[0042] Preferably, the reaction temperature in step b is 80° C. and the reaction time is 60 hours.

[0043] Preferably, step b further comprises refining the crude high molecular weight polymer by dialysis, wherein the dialysate is acetonitrile.

[0044] A fourth aspect of the present invention provides a method for preparing a supramolecular assembly, which specifically comprises the following operations:

[0045] The hydrazine-naphthalene imide functionalized column [5] aromatic hydrocarbon is dissolved in an acetonitrile-chloroform mixed solvent to prepare a hydrazine-naphthalene imide functionalized column [5] aromatic hydrocarbon stock solution;

[0046] Dissolving a polymer having a structural formula as shown in Formula II in an acetonitrile-chloroform mixed solvent to prepare a polymer stock solution;

[0047] The hydrazine naphthalimide functionalized column [5] aromatic hydrocarbon stock solution and the high molecular weight polymer stock solution are added to an acetonitrile-chloroform mixed solvent equivalent to 29 to 49 times the sum of the volumes of the two stock solutions, and allowed to stand for at least 30 minutes to obtain a solution of the supramolecular assembly.

[0048] In combination with the fourth aspect, the concentration of the aromatic hydrocarbon stock solution of the hydrazine naphthalimide functionalized column [5] is 2×10 -3 mol / L.

[0049] In combination with the fourth aspect, the concentration of the polymer stock solution is 2×10 -3 mol / L.

[0050] In combination with the fourth aspect, the volume ratio of acetonitrile to chloroform in the acetonitrile-chloroform mixed solvent is (0.8-1.2):1, preferably 1:1.

[0051] The fifth aspect of the present invention provides a thin film sensor, which is made of the above-mentioned hydrazine-naphthalene imide functionalized column [5] aromatic hydrocarbon and a high molecular polymer with a structural formula as shown in Formula II.

[0052] A sixth aspect of the present invention provides a method for preparing a thin film sensor, which specifically includes the following operations:

[0053] The hydrazine-naphthalene imide functionalized column [5] aromatic hydrocarbon and the high molecular polymer having a structural formula as shown in Formula II are dissolved in an acetonitrile-chloroform mixed solvent to prepare a hydrazine-naphthalene imide functionalized column [5] aromatic hydrocarbon stock solution and a high molecular polymer stock solution;

[0054] The hydrazine naphthalimide functionalized column [5] aromatic hydrocarbon stock solution and the high molecular polymer stock solution are mixed, allowed to stand for 30 to 60 minutes, and then drop-coated on the surface of a quartz glass sheet. After the solvent evaporates, the thin film sensor is obtained.

[0055] In combination with the sixth aspect, the concentration of the aromatic hydrocarbon stock solution of the hydrazine naphthalimide functionalized column [5] is 1×10 -2 mol / L.

[0056] In combination with the sixth aspect, the concentration of the polymer stock solution is 1×10 -2 mol / L.

[0057] In combination with the sixth aspect, the volume ratio of acetonitrile to chloroform in the acetonitrile-chloroform mixed solvent is (0.8-1.2):1, preferably 1:1.

[0058] A seventh aspect of the present invention provides the use of the thin film sensor or the thin film sensor manufactured according to the above-mentioned preparation method in the detection and identification of gaseous formaldehyde. BRIEF DESCRIPTION OF THE DRAWINGS

[0059] Figure 1 The stability spectra of the solution-state supramolecular assembly (left) and thin film sensor (right) in Test Example 1 of the present invention are shown;

[0060] Figure 2 This is a fluorescence spectrum of the supramolecular assembly in Test Example 1 of the present invention sensing formaldehyde in solution;

[0061] Figure 3 This is the specific spectrum of the supramolecular assembly in Test Example 1 of the present invention sensing formaldehyde in solution;

[0062] Figure 4 This is an optical photograph of the supramolecular assembly in Test Example 1 of the present invention in solution for common aldehydes and formaldehyde at 365 nm;

[0063] Figure 5 This is the fluorescence spectrum of the thin film sensor sensing gaseous formaldehyde in Test Example 1 of the present invention;

[0064] Figure 6 This is a visual detection diagram of gaseous formaldehyde by the thin film sensor in Test Example 1 of the present invention at different times. DETAILED DESCRIPTION

[0065] In order to make the purpose, technical solutions and advantages of the present invention more clearly understood, the present invention is further described in detail below in conjunction with specific embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not intended to limit the present invention.

[0066] Formaldehyde has posed a serious threat to human health and the ecological environment. Currently, the detection methods for formaldehyde include the following: chromatography, spectrophotometry, electrochemical sensing, fluorescent probes, etc., but there are certain limitations in the detection of formaldehyde.

[0067] In order to solve the above problems, the embodiment of the present invention provides a hydrazine-naphthalene imide functionalized column [5] arene and its preparation method. The hydrazine-naphthalene imide functionalized column [5] arene has a column [5] arene with a specific cavity as the skeleton and hydrazine-naphthalene imide as the detection group. It can be used as a fluorescent probe to detect formaldehyde and has the advantages of high sensitivity, specificity and no limitation of instrument conditions. Experiments have shown that the supramolecular assembly constructed by the hydrazine-naphthalene imide functionalized column [5] arene has a certain stability in air and has no response to other aldehydes. With the hydrazine-naphthalene imide functionalized column [5] arene as the main body, it can not only detect formaldehyde, but also recognize specific guest molecules to form a supramolecular assembly.

[0068] The embodiment of the present invention also provides a supramolecular assembly and a preparation method thereof, wherein the supramolecular assembly is made of the above-mentioned hydrazine-naphthaleneimide functionalized column [5] aromatic hydrocarbon and a high molecular polymer.

[0069] The embodiment of the present invention also provides a thin film sensor and its preparation method and application, which is made of the above-mentioned hydrazine naphthalimide functionalized column [5] aromatic hydrocarbon and a high molecular polymer with a structural formula as shown in Formula II, and can solve the problems of high formaldehyde detection limit, long response time and difficulty in carrying existing detection methods.

[0070] The embodiments of the present invention are further described below with reference to a number of embodiments.

[0071] Example 1

[0072] This embodiment provides a hydrazine-naphthalene imide functionalized pillar [5] aromatic hydrocarbon, the structural formula of which is shown in Formula I:

[0073]

[0074] Formula I.

[0075] The steps of its preparation method are as follows:

[0076] (1) 0.99 g (1 mmol) of column[5]arene and 0.42 g (6 mmol) of sodium azide were dissolved in a mixture of 25 ml of N,N-dimethylformamide and 2.5 ml of water. The mixture was reacted at 80°C for 3 hours. 1.75 mM aqueous sodium sulfide nonahydrate solution was then added and the reaction was continued for 4 hours. The mixture was cooled to room temperature. The reaction solution was poured into 250 ml of water and filtered to obtain a white solid (yield 87.2%). The molar ratio of column[5]arene, sodium azide, and sodium sulfide nonahydrate was 1:6:9.

[0077] (2) The white solid obtained in step (1), 0.85 g (3 mmol) of 4-bromo-1,8-naphthalenedicarboxylic anhydride and 40 ml of anhydrous ethanol were added to a round-bottom flask, reacted at 80°C for 14 hours, cooled, filtered, and the filter cake was purified by column chromatography using a dichloromethane:methanol ratio of 500:1 as the eluent. The eluted fractions were collected and the solvent was removed to obtain a yellow solid (yield 39.1%).

[0078] (3) The yellow solid obtained in step (2) was dissolved in 100 ml of hydrazine hydrate, heated to 130° C., reacted for 3 hours, cooled, filtered, and the filter cake was recrystallized in n-hexane to obtain hydrazine-naphthalene imide functionalized column [5] aromatic hydrocarbon.

[0079] The aromatic product of the hydrazine-naphthalimide functionalized column [5] prepared by the above steps is a yellow powder with a yield of 68.4%. The results of nuclear magnetic resonance detection are as follows: 1 H NMR (400 MHz, DMSO): δ 9.14 (s, 2H), 8.62 (d, J = 8.3Hz, 2H), 8.43 (d, J = 7.2 Hz, 2H), 8.30 (d, J = 8.6 Hz, 2H), 7.64 (t, J = 7.9Hz, 2H), 7.25 (d, J = 8.6 Hz, 2H), 6.73 (dd, J = 9.9, 7.2 Hz, 10H), 4.71 (s,3H), 4.11 (d, J = 6.8 Hz, 4H), 3.84 (d, J = 18.2 Hz, 4H), 3.66–3.49 (m, 34H), 1.84 (dd, J = 22.0, 6.1 Hz, 8H); 13C NMR (100 MHz, DMSO): δ 164.32, 163.45, 153.63, 150.25, 149.64, 134.69, 131.05, 129.80, 128.74, 128.21, 124.58, 122.20, 118.94, 114.53, 113.61, 107.89, 104.51, 68.09, 55.80, 55.67, 31.24, 29.33, 27.49, 25.28, 22.32, 14.40. Mass spectral data are: HRMS (MALDI-TOF) for C 75 H 76 N6O 14 ([M-2NHNH2+H2O+H] + )calcd.1241.5010, found 1241.0772. ([M-2NHNH2+H2O+K+H] + )calcd. 1280.4647, found1280.1967.

[0080] Example 2

[0081] This embodiment provides a method for preparing hydrazine-naphthalene imide functionalized column [5] aromatic hydrocarbons, the steps of which are as follows:

[0082] (1) 0.99 g (1 mmol) of column[5]arene and 0.28 g (4 mmol) of sodium azide were dissolved in a mixture of 20 ml of N,N-dimethylformamide and 2 ml of water. The mixture was reacted at 60°C for 3 hours. 1 mM aqueous sodium sulfide nonahydrate solution was then added and the reaction was continued for 3 hours. The mixture was then cooled to room temperature. The reaction solution was poured into 200 ml of water and filtered to obtain a white solid (yield 86.7%). The molar ratio of column[5]arene, sodium azide, and sodium sulfide nonahydrate was 1:4:8.

[0083] (2) The white solid obtained in step (1), 0.85 g (3 mmol) of 4-bromo-1,8-naphthalenedicarboxylic anhydride and 30 ml of anhydrous ethanol were added to a round-bottom flask, reacted at 60°C for 15 hours, cooled, filtered, and the filter cake was purified by column chromatography using dichloromethane:methanol = 500:1 as the eluent. The eluted fractions were collected and the solvent was removed to obtain a yellow solid (yield 38.6%).

[0084] (3) The yellow solid obtained in step (2) was dissolved in 75 ml of hydrazine hydrate, heated to 140° C., reacted for 3 hours, cooled, filtered, and the filter cake was recrystallized in n-hexane to obtain hydrazine-naphthalene imide functionalized column [5] aromatic hydrocarbon.

[0085] Example 3

[0086] This embodiment provides a method for preparing hydrazine-naphthalene imide functionalized column [5] aromatic hydrocarbons, the steps of which are as follows:

[0087] (1) 0.99 g (1 mmol) of column[5]arene and 0.56 g (8 mmol) of sodium azide were dissolved in a mixture of 30 ml of N,N-dimethylformamide and 3 ml of water. The mixture was reacted at 80°C for 2 hours. A 2.5 mM aqueous sodium sulfide nonahydrate solution was then added and the reaction was continued for 5 hours. The mixture was then cooled to room temperature. The reaction solution was poured into 300 ml of water and filtered to obtain a white solid (yield 87.0%). The molar ratio of column[5]arene, sodium azide, and sodium sulfide nonahydrate was 1:8:9.

[0088] (2) The white solid obtained in step (1), 1.13 g (4 mmol) of 4-bromo-1,8-naphthalenedicarboxylic anhydride and 50 ml of anhydrous ethanol were added to a round-bottom flask, reacted at 90°C for 13 hours, cooled, filtered, and the filter cake was purified by column chromatography using dichloromethane:methanol = 500:1 as the eluent. The eluted fractions were collected and the solvent was removed to obtain a yellow solid (yield 38.8%).

[0089] (3) The yellow solid obtained in step (2) was dissolved in 50 ml of hydrazine hydrate, heated to 120° C., reacted for 4 hours, cooled, filtered, and the filter cake was recrystallized in n-hexane to obtain hydrazine-naphthalene imide functionalized column [5] aromatic hydrocarbon.

[0090] Example 4

[0091] This embodiment provides a supramolecular assembly, which is made of the hydrazine-naphthalene imide functionalized column [5] aromatic hydrocarbon prepared in Example 1 and a high molecular polymer.

[0092] 1. Preparation of polymers

[0093] The structural formula of the high molecular polymer is shown in Formula II:

[0094]

[0095] Formula II.

[0096] The preparation steps of the high molecular polymer are:

[0097] (1) 12 g (10 mmol) of 4-hydroxystyrene, 1.6 g (10 mmol) of 5-bromopentanenitrile, 5.5 g (40 mmol) of anhydrous potassium carbonate, 0.25 g (1.5 mmol) of potassium iodide (molar ratio of 1:1:4:0.15) were dissolved in 100 ml of acetonitrile, and refluxed at 60°C for 36 hours under a nitrogen atmosphere. After cooling, the reaction solution was filtered, and the filtrate was collected. The filtrate was purified by column chromatography using pure dichloromethane as an eluent, and the eluted fraction was collected. After removing the solvent, a yellow oily liquid was obtained (yield 88.3%).

[0098] (2) The yellow oily liquid obtained in step (1), 8.14 g (80 mmol) of methyl methacrylate, 0.01 g (0.03 mmol) of 2-(dodecyltrithiocarbonate)-2-methylpropionic acid, and 0.0054 g (0.03 mmol) of azobisisobutyronitrile (molar ratio of 1:8:0.003:0.003) were dissolved in a round-bottom flask with 310 ml of anhydrous tetrahydrofuran as a solvent, and heated to 80°C for 60 hours. After cooling, the reaction solution was poured into 250 ml of n-hexane, and filtered to collect the filter cake. The filter cake was dissolved in 25 ml of acetonitrile, and then introduced into a dialysis bag (44 mm in diameter, 5000 in molecular weight cut-off). The dialysis bag was sealed, and then immersed in 900 ml of pure acetonitrile. The dialysis solution was replaced every 8 hours, and dialysis was performed for 48 hours. After dialysis, the polymer was obtained.

[0099] The polymer product prepared by the above procedure was a white powder, and the yield was 58%. The results of nuclear magnetic resonance detection are as follows: 1 H NMR (400 MHz, CD3CN): δ 6.97-6.70 (m, 2H), 3.94 (d, J = 18.1 Hz, 1H), 3.54 (d, J = 27.4 Hz, 35H), 2.47 (s, 2H). The value of X / Y is 17.5 / 1, X = 483.14, Y = 28.42, PDI = 1.18, M n = 54090 as measured by NMR and GPC.

[0100] 2. Construction of supramolecular assemblies

[0101] The hydrazinonaphthalimide-functionalized pillar[5]arene (host 1) prepared from Example 1 and the polymer (guest 2) prepared from the above procedure of this example were each dissolved in a mixed solvent of acetonitrile-chloroform (v:v = 1:1) to prepare 2 x 10 -3mol / L stock solution; 30 μL of each of the two stock solutions was added to 2940 μL of acetonitrile-chloroform (v:v = 1:1) mixed solvent, and the mixture was allowed to stand at room temperature for 30 minutes to prepare the supramolecular assembly.

[0102] Example 5

[0103] This example provides a supramolecular assembly made of hydrazinonaphthalimide functionalized pillar[5]arene of Example 2 and a polymer.

[0104] 1. Preparation of the polymer

[0105] The structural formula of the polymer is shown as Formula II.

[0106] The preparation steps of the polymer are as follows:

[0107] (1) 12 g (10 mmol) of 4-hydroxystyrene, 2.0 g (12 mmol) of 5-bromopentanenitrile, 6.9 g (50 mmol) of anhydrous potassium carbonate, and 0.29 g (1.75 mmol) of potassium iodide (molar ratio of 1:1.25:5:0.175) were dissolved in 80 ml of acetonitrile, and the mixture was refluxed at 60°C for 40 hours under a nitrogen atmosphere. After cooling, the mixture was filtered, and the filtrate was collected. The filtrate was purified by column chromatography using pure dichloromethane as the eluent, and the eluted fractions were collected. After removing the solvent, a yellow oily liquid was obtained (yield 88.1%).

[0108] (2) The yellow oily liquid obtained in step (1), 6.1 g (60 mmol) of methyl methacrylate, 0.007 g (0.02 mmol) of 2-(dodecyltrithiocarbonate)-2-methylpropionic acid, and 0.0036 g (0.02 mmol) of azobisisobutyronitrile (molar ratio of 1:6:0.002:0.002) were placed in a round-bottom flask with 280 ml of anhydrous tetrahydrofuran as the solvent, and the mixture was heated to 70°C and reacted for 65 hours. After cooling, the reaction solution was poured into 200 ml of n-hexane, and the mixture was filtered to collect the filter cake. The filter cake was dissolved in 20 ml of acetonitrile, and the solution was placed in a dialysis bag (44 mm in diameter and 5000 in molecular weight cut-off). The dialysis bag was sealed, and pure acetonitrile was used as the dialysate. The dialysis bag was placed in 800 ml of pure acetonitrile, and the dialysate was replaced every 12 hours. After dialysis for 48 hours, the polymer was obtained.

[0109] 2. Construction of the supramolecular assembly

[0110] The hydrazinonaphthalimide functionalized pillar[5]arene (host 1) obtained in Example 2 and the polymer (guest 2) obtained in the above step of this example were dissolved in acetonitrile-chloroform (v:v = 1:1) mixed solvent to prepare 2 x 10 -3mol / L stock solution; 40 μL of each of the two stock solutions was added to 2920 μL of acetonitrile-chloroform (v:v=1:1) mixed solvent and allowed to stand at room temperature for 50 minutes to prepare the supramolecular assembly.

[0111] Example 6

[0112] This embodiment provides a supramolecular assembly, which is made of the hydrazine-naphthalene imide functionalized column [5] aromatic hydrocarbon prepared in Example 3 and a high molecular polymer.

[0113] 1. Preparation of polymers

[0114] The structural formula of the high molecular weight polymer is shown in Formula II.

[0115] The preparation steps of the high molecular polymer are:

[0116] (1) 12 g (10 mmol) of 4-hydroxystyrene, 2.4 g (15 mmol) of 5-bromovaleronitrile, 8.3 g (60 mmol) of anhydrous potassium carbonate, and 0.33 g (2 mmol) of potassium iodide (molar ratio of 1:1.5:6:0.20) were dissolved in 120 ml of acetonitrile. The mixture was refluxed at 80°C for 30 hours under a nitrogen atmosphere. The mixture was cooled, filtered, and the filtrate was collected. The filtrate was purified by column chromatography using pure dichloromethane as the eluent. The eluted fractions were collected and the solvent was removed to obtain a yellow oily liquid (yield 87.6%).

[0117] (2) The yellow oily liquid obtained in step (1), 9.16 g (90 mmol) of methyl methacrylate, 0.013 g (0.04 mmol) of 2-(dodecyltrithiocarbonate)-2-methylpropionic acid, and 0.009 g (0.05 mmol) of azobisisobutyronitrile (molar ratio of 1:9:0.004:0.005) were placed in a round-bottom flask with 340 ml of anhydrous tetrahydrofuran as solvent, heated to 90°C, reacted for 50 hours, cooled, and the reaction solution was added to 300 ml of n-hexane, filtered, and the filter cake was collected. The filter cake was dissolved in 30 ml of acetonitrile and placed in a dialysis bag (diameter 44 mm, cut-off molecular weight 5000). The dialysis bag was sealed and placed in 1000 ml of pure acetonitrile with pure acetonitrile as the dialysis solution. The dialysis solution was replaced every 4 hours. After dialysis for 48 hours, the polymer was obtained.

[0118] 2. Construction of supramolecular assemblies

[0119] The hydrazine-naphthalimide functionalized column [5]arene (host 1) prepared in Example 3 and the high molecular weight polymer (guest 2) prepared in the above steps of this example were dissolved in acetonitrile-chloroform (v:v=1:1) mixed solvent to prepare 2×10 -3mol / L stock solutions; 50 μL of each of the two stock solutions was added to 2900 μL of a mixed solvent of acetonitrile-chloroform (v:v=1:1) and allowed to stand at room temperature for 60 minutes to prepare supramolecular assemblies.

[0120] Example 7

[0121] This embodiment provides a thin film sensor made of the hydrazine-naphthalene imide functionalized column [5] aromatic hydrocarbon prepared in Example 1 and the high molecular polymer prepared in Example 4. The preparation process is as follows:

[0122] The obtained hydrazine naphthalimide functionalized column [5]arene (host 1) obtained in Example 1 and the high molecular weight polymer (guest 2) obtained in Example 4 were dissolved in acetonitrile-chloroform (v:v=1:1) mixed solvent to prepare 1×10 -2 mol / L stock solution; the two stock solutions were mixed and allowed to stand at room temperature for 30 minutes; 50 μL of the mixed stock solution after standing was dropped on the surface of the quartz glass sheet, and the solvent was evaporated to obtain a thin film sensor.

[0123] Example 8

[0124] This embodiment provides a thin film sensor made of the hydrazine-naphthalene imide functionalized column [5] aromatic hydrocarbon prepared in Example 2 and the high molecular polymer prepared in Example 5. The preparation process is as follows:

[0125] The obtained hydrazine naphthalimide functionalized column [5]arene (host 1) obtained in Example 1 and the high molecular weight polymer (guest 2) obtained in Example 4 were dissolved in acetonitrile-chloroform (v:v=1:1) mixed solvent to prepare 1×10 -2 mol / L stock solution; the two stock solutions were mixed and allowed to stand at room temperature for 45 minutes; 35 μL of the mixed stock solution after standing was dropped on the surface of the quartz glass sheet, and the solvent was evaporated to obtain a thin film sensor.

[0126] Example 9

[0127] This embodiment provides a thin film sensor made of the hydrazine-naphthalene imide functionalized column [5] aromatic hydrocarbon prepared in Example 3 and the high molecular polymer prepared in Example 6. The preparation process is as follows:

[0128] The obtained hydrazine naphthalimide functionalized column [5]arene (host 1) obtained in Example 1 and the high molecular weight polymer (guest 2) obtained in Example 4 were dissolved in acetonitrile-chloroform (v:v=1:1) mixed solvent to prepare 1×10 -2 mol / L stock solution; the two stock solutions were mixed and allowed to stand at room temperature for 60 minutes; 20 μL of the mixed stock solution after standing was dropped on the surface of the quartz glass sheet, and the solvent was evaporated to obtain a thin film sensor.

[0129] Test Example 1

[0130] In order to verify the technical effect of the present invention, this test example investigated the detection behavior of the supramolecular assembly constructed in Example 4 and the thin film sensor prepared in Example 7 towards formaldehyde.

[0131] The stability fluorescence spectra of the supramolecular assembly in the acetonitrile-chloroform mixed solvent obtained in Example 4 and the thin film sensor obtained in Example 7 are shown in FIG. Figure 1 As shown in the figure, it can be seen that the supramolecular assembly exhibits excellent stability in both solution and film states. In subsequent applications, it does not need to be prepared on the spot, is easy to use, and the film state is easy to carry.

[0132] The fluorescence spectrum of the solution-state supramolecular assembly obtained in Example 4 for formaldehyde sensing is shown in FIG. Figure 2 As shown in the figure, 0.1 μM formaldehyde can cause the fluorescence of the assembly to increase. With the increase of formaldehyde concentration, the fluorescence intensity gradually increases. The calculated detection limit is 2.38×10 -8 mol / L.

[0133] The specificity of the supramolecular assembly in solution obtained in Example 4 for sensing formaldehyde was tested by using glyoxal (2), p-hydroxybenzaldehyde (3), p-nitrobenzaldehyde (4), benzaldehyde (5), acetaldehyde (6), m-bromobenzaldehyde (7), p-methylbenzaldehyde (8), p-chlorobenzaldehyde (9), salicylaldehyde (10), p-bromobenzaldehyde (12), p-terephthalaldehyde (12), o-chlorobenzaldehyde (13), n-propionaldehyde (14), and formaldehyde (15) (1 is a blank control, only the assembly), as shown in the spectrum. Figure 3 As shown in the optical photograph Figure 4 As shown in the figure, it can be seen that only formaldehyde can turn on the fluorescence of the assembly solution, and other aldehydes will not interfere with the experimental results.

[0134] The thin film sensor obtained in Example 7 was placed in formaldehyde gas with different concentrations. The fluorescence spectra of the thin film sensor sensing gaseous formaldehyde were as follows: Figure 5 As shown in the figure, it can be seen that the fluorescence of the film gradually increases with the increase of formaldehyde concentration, and its calculated detection limit for gaseous formaldehyde is 0.078 mg / L, which is lower than the national residential standard (0.08 mg / L).

[0135] The thin film sensor obtained in Example 7 was placed in a 0.5% formaldehyde atmosphere to observe the changes in its fluorescence at different times. The visual detection diagram of the thin film sensor for gaseous formaldehyde at different times is shown in FIG. Figure 6As shown in the figure, it can be seen that the thin film sensor shows obvious fluorescence changes in nearly 1 minute. Therefore, the film can realize visual sensing of formaldehyde in the air, which makes it possible to be applied in real life and also provides a new strategy for rapid detection of formaldehyde.

[0136] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions or improvements made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.

Claims

1. A supramolecular assembly, characterized in that: The supramolecular assembly is made of hydrazine-naphthalene imide functionalized pillar [5] aromatic hydrocarbon and a high molecular polymer. The structural formula of the hydrazine-naphthalene imide functionalized pillar [5] aromatic hydrocarbon is shown in Formula I: Formula I; The structural formula of the high molecular polymer is shown in Formula II: Formula II; X=483.14, Y=28.

42.

2. The supramolecular assembly according to claim 1, characterized in that The preparation method of the hydrazine-naphthalimide functionalized column [5] aromatic hydrocarbon specifically comprises the following steps: S1. Dissolve column [5] aromatic hydrocarbon and sodium azide in a mixture of N,N-dimethylformamide and water, react at 60-80°C for 2-3 hours, then add sodium sulfide nonahydrate aqueous solution, continue to react for 3-5 hours, cool to room temperature, put the reaction solution into water, separate the solid and liquid, and obtain a white solid; The structural formula of the pillar[5]arene is as follows: S2. Reacting the white solid obtained in S1, 4-bromo-1,8-naphthalene dicarboxylic anhydride, and anhydrous ethanol at 60-90° C. for 13-15 hours, cooling, and solid-liquid separation. Purifying the resulting solid phase by column chromatography using a dichloromethane:methanol ratio of 500:1 as eluent, collecting the eluted fractions, and removing the solvent to obtain a yellow solid. S3. Dissolve the yellow solid obtained in S2 in hydrazine hydrate, heat to 120-140° C., react for 3-4 hours, cool, and separate the solid and liquid. The resulting solid phase is the crude product of the hydrazine-naphthaleneimide functionalized column [5] aromatic hydrocarbon.

3. The supramolecular assembly according to claim 2, wherein The molar ratio of the column [5] aromatic hydrocarbon, sodium azide, and sodium sulfide nonahydrate in S1 is 1:(4-8):(8-9); and / or The molar ratio of the pillar [5] aromatic hydrocarbon in S1 to the 4-bromo-1,8-naphthalene dicarboxylic anhydride in S2 is 1:(3-4); and / or The molar ratio of the pillar [5] aromatic hydrocarbon in S1 to the hydrazine hydrate in S3 is 1:(1000-2000); and / or S3 further comprises recrystallizing the obtained solid phase in n-hexane.

4. The supramolecular assembly according to claim 1, characterized in that The preparation method of the high molecular polymer specifically comprises the following steps: Step a, dissolving 4-hydroxystyrene, 5-bromovaleronitrile, anhydrous potassium carbonate, and potassium iodide in acetonitrile, reflux at 60-80° C. for 30-40 hours under an inert atmosphere, cooling, solid-liquid separation, collecting the liquid phase, and purifying the liquid phase by column chromatography with pure dichloromethane as the eluent, collecting the eluted fraction, and removing the solvent to obtain a yellow oily liquid; Step b, mixing the yellow oily liquid obtained in step a with methyl methacrylate, 2-(dodecyltrithiocarbonate)-2-methylpropionic acid, and azobisisobutyronitrile in anhydrous tetrahydrofuran, heating to 70-90° C., reacting for 50-65 hours, cooling, adding the reaction solution into n-hexane, performing solid-liquid separation, and collecting the solid phase to obtain the crude polymer.

5. The supramolecular assembly according to claim 4, wherein The molar ratio of 4-hydroxystyrene, 5-bromovaleronitrile, anhydrous potassium carbonate and potassium iodide in step a is 1:(1-1.5):(4-6):(0.15-0.20); and / or The molar ratio of the 4-hydroxystyrene described in step a to the methyl methacrylate, 2-(dodecyltrithiocarbonate)-2-methylpropionic acid, and azobisisobutyronitrile described in step b is 1:(6-9):(0.002-0.004):(0.002-0.005); and / or Step b further comprises refining the crude high molecular polymer by dialysis, wherein the dialysate is acetonitrile.

6. A method for preparing a supramolecular assembly, characterized in that: The specific operations include: Dissolving the hydrazine-naphthalene imide functionalized column [5] aromatic hydrocarbons described in claim 1 in an acetonitrile-chloroform mixed solvent to prepare a hydrazine-naphthalene imide functionalized column [5] aromatic hydrocarbons stock solution; Dissolving the high molecular weight polymer described in claim 1 in an acetonitrile-chloroform mixed solvent to prepare a high molecular weight polymer stock solution; The hydrazine naphthalimide functionalized column [5] aromatic hydrocarbon stock solution and the high molecular weight polymer stock solution are added to an acetonitrile-chloroform mixed solvent equivalent to 29 to 49 times the sum of the volumes of the two stock solutions, and allowed to stand for at least 30 minutes to obtain a solution of the supramolecular assembly.

7. A thin film sensor, characterized in that: The invention is made of the hydrazine-naphthaleneimide functionalized column [5] aromatic hydrocarbon described in claim 1 and the high molecular polymer described in claim 1.

8. A method for preparing a thin film sensor, characterized in that: Specifically, the steps include: dissolving the hydrazine-naphthalimide functionalized column [5] aromatic hydrocarbon described in claim 1 and the high molecular polymer described in claim 1 in an acetonitrile-chloroform mixed solvent to prepare a hydrazine-naphthalimide functionalized column [5] aromatic hydrocarbon stock solution and a high molecular polymer stock solution; The hydrazine naphthalimide functionalized column [5] aromatic hydrocarbon stock solution and the high molecular polymer stock solution are mixed, allowed to stand for 30 to 60 minutes, and then drop-coated on the surface of a quartz glass sheet. After the solvent evaporates, the thin film sensor is obtained.

9. Use of the thin film sensor according to claim 7 or the thin film sensor prepared by the preparation method according to claim 8 in the detection and identification of gaseous formaldehyde.

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