A bisquinoline functionalized naphthalene diimide derivative and its preparation and application in detecting and separating hydrazine hydrate

Abstract

The invention discloses a bisquinoline functionalized naphthalimide derivative. Under N2 gas conditions, 1,4,5,8-naphthalene tetracarboxylic anhydride and 2-(quinoline-8-oxy) acetohydrazide are added to an anhydrous DMF solution, stirred and dissolved at 135-145°C, and then the solution is vigorously stirred at 135-145°C for 15-20 h under continuous reflux conditions, cooled to room temperature, filtered and collected, washed with anhydrous methanol, and finally vacuum dried to obtain 8-QP. The compound can detect and adsorb and separate hydrazine hydrate vapor through multi-channel under the synergistic effect of quinoline and naphthalimide functional groups. The crystals formed by 8-QP can detect hydrazine hydrate vapor with high selectivity, and the crystals have good adsorption and separation properties for hydrazine hydrate vapor. 8-QP can also form supramolecular organic gels in dimethyl sulfoxide and water binary solutions, and the 8-QP gel can realize multi-channel detection of hydrazine hydrate vapor.

Description

Technical Field

[0001] The present invention relates to a bisquinoline functionalized naphthalimide derivative and a preparation method thereof, and also relates to its application in hydrazine hydrate (DH) and hydrazine hydrate vapor detection and adsorption separation; the present invention also relates to the use of 8-QP to prepare supramolecular organic gel for naked eye detection and fluorescence detection of hydrazine hydrate. The present invention belongs to the field of chemical synthesis and material preparation, and the field of toxic gas detection, adsorption and separation. Background Art

[0002] Hydrazine hydrate (also known as hydrazine) is a widely used raw material and intermediate in the chemical industry. It has strong reducing and alkalinity and has important applications in the fields of medicine, agriculture, pesticides, dyes and antioxidants. However, it should be noted that hydrazine hydrate is also highly toxic and potentially carcinogenic. Due to its good water solubility, its leakage will pose a chain threat to the environment, ecology and human health, such as water pollution, soil corrosion, food safety, and ultimately lead to human liver, lung and nervous system diseases and even death. It is then absorbed by the human body and causes lasting damage to cells, tissues and nerves. In addition, hydrazine hydrate vapor leakage can also cause catastrophic explosions in chemical facilities. Therefore, real-time detection and adsorption and separation of hydrazine hydrate in water and air are crucial in chemical production and environmental protection. Among the currently reported hydrazine hydrate detection methods, instrumental detection methods are limited by the need to use expensive instruments. In addition, most of the reported fluorescent sensors can only be used for hydrazine hydrate detection, but cannot adsorb and separate hydrazine hydrate, while other reported hydrazine hydrate adsorption and separation materials cannot be used for hydrazine hydrate detection at the same time. Therefore, materials that are easy to synthesize, low-cost, and easy to use and can simultaneously achieve high-sensitivity detection and efficient adsorption of hydrazine hydrate and its vapor have important demands and application prospects in the field of chemical production. In the present invention, we designed and synthesized a bisquinoline functionalized naphthalimide derivative (8-QP). The material can detect and adsorb and separate hydrazine hydrate and hydrazine hydrate vapor in multiple channels, and has specific selectivity and high sensitivity. The material has the advantages of being easy to synthesize and easy to apply. Summary of the invention

[0003] The purpose of the present invention is to provide a supramolecular intelligent material capable of multi-channel detection and adsorption of hydrazine hydrate;

[0004] Another object of the present invention is to provide a method for synthesizing the above-mentioned 8-QP functional molecule;

[0005] 1. Bisquinoline functionalized naphthalene diimide derivatives and their preparation

[0006] The molecular formula of the bisquinoline functionalized naphthalene diimide derivative of the present invention is: 35 H 22 N6O8, marked as: 8-QP, its structural formula is:

[0007]

[0008] Preparation of 8-QP: Under N2 gas conditions, 1,4,5,8-naphthalenetetracarboxylic anhydride and 2-(quinoline-8-oxy)acethydrazide Q2 were added to anhydrous DMF solution, stirred and dissolved at 135~145℃, and then the solution was vigorously stirred at 135~145℃ under continuous reflux conditions for 15~20 h, cooled to room temperature, and the precipitate was collected by filtration, washed with anhydrous methanol, and finally dried in vacuum to obtain the target functional molecule 8-QP.

[0009] The synthetic route of 8-QP is:

[0010]

[0011] The mass spectrum and hydrogen spectrum of the functional molecule 8-QP are shown in Figure 1 , Figure 2 .

[0012] 2. 8-QP Crystalline Powder Detection and Adsorption of Hydrazine Hydrate Vapor

[0013] 1. Structure of 8-QP crystal

[0014] The functional molecule 8-QP was slowly evaporated at room temperature in a dimethyl sulfoxide solution to obtain dark orange crystals with a porous structure and a porosity of 32.8%. 8-QP has intramolecular hydrogen bonds ( Figure 3 a). This host is assembled into a pseudo-cavity with other 8 hosts through CH⋯O interaction topology ( Figure 3 b), forming an empty one-dimensional channel along the crystallographic a-axis. Figure 3 As shown in Figure c, the center-to-center distance between the quinoline ring and the naphthalene ring on the two main bodies is 3.4439 Å, indicating that the three 8-QP molecules form a sandwich trimer through π···π stacking, and the calculated solvent accessible volume of the crystalline 8-QP is estimated to be 3056.66 Å 3 .

[0015] 2. Recognition and adsorption separation of hydrazine hydrate by 8-QP crystal powder

[0016] Figure 4 The 8-QP supramolecular crystal of the present invention can selectively detect and adsorb and separate hydrazine hydrate. When the 8-QP crystal powder is exposed to the vapors of hydrazine hydrate, ethanolamine, ammonia water, cyclohexylamine, 2-n-butylamine, ethylenediamine, 1,6-hexanediamine, triethylamine, and trimethylamine, only the vapor of hydrazine hydrate can cause the crystal powder to change color. Only the vapor of hydrazine hydrate can cause the color of the 8-QP crystal powder to change from orange to black. Other vapors cannot cause the 8-QP crystal powder to undergo such a change (e.g. Figure 4a), which fully demonstrates that 8-QP crystal has high selectivity for hydrazine hydrate vapor and can realize selective naked eye colorimetric identification of hydrazine hydrate vapor.

[0017] 8-QP crystals have good adsorption and separation properties for hydrazine hydrate vapor, and the molar adsorption capacity is 43%. 0.0273g of 8-QP crystals were weighed by the weighing method to adsorb DH. After adsorbing DH under the same conditions, the mass of 8-QP increased by 0.0009 g, and the molar adsorption rate was 43%.

[0018] In addition, when heated to 60-90 °C, the color of the adsorbed 8-QP crystals can be changed to the original orange (e.g. Figure 4 b), thereby separating hydrazine hydrate vapor from the adsorbed 8-QP crystals. These results indicate that 8-QP crystals have the cyclic availability for hydrazine hydrate vapor.

[0019] 3. Preparation of 8-QP supramolecular organogel and detection of hydrazine hydrate

[0020] Preparation of 8-QP supramolecular organogel: 8-QP was added to the DMSO-H2O binary system, heated in the range of 100-150°C until 8-QP was completely dissolved, and cooled to room temperature to form a uniform and stable supramolecular organogel; in the DMSO-H2O binary system, the volume ratio of DMSO and H2O was 8:2.

[0021] The supramolecular organogel can detect and adsorb hydrazine hydrate vapor. The minimum critical gel concentration (CGC) is 0.6% (w / v, 1 mg / mL = 1%). When 8-QP gel is exposed to hydrazine hydrate vapor, the gel color changes from yellow to black, the fluorescence is quenched, and the gel state is transformed into a sol state (e.g. Figure 5 The process is irreversible, and the changes in the color, fluorescence, and state of the gel enable multi-channel detection of hydrazine hydrate vapor by 8-QP-G gel.

[0022] Figure 6 The gelation mechanism of 8-QP gel was investigated by using rheological laser laboratory diffusion wave spectroscopy. The elastic index (EI) was plotted against time. Figure 6 a) and solid-liquid equilibrium (SLB) value ( Figure 6 b). Figure 6 As can be seen from b, the platform height of DQ8-G after adsorption of DH decreases, indicating that the viscoelasticity of DQ8-G decreases. The value of SLB greater than 0.5 means the dominant influence of liquid behavior, and less than 0.5 means the dominant influence of solid behavior, indicating that fluid behavior dominates the gel and the gel network is broken. Figure 6As shown in c, the lower the platform of mean square displacement (MSD), the higher the elasticity of the gel. Therefore, the increase in the platform of DQ8-G after adsorption of DH vapor indicates that the elasticity of DQ8-G decreases significantly. In order to observe the viscoelastic changes throughout the gelation process, in addition, Figure 6 The elastic modulus (G') shown in d is used to determine the elastic energy temporarily stored in the soft material to resist external forces. The elastic modulus (G') of DQ8-G+DH was tested in the sweep range of 0.1 to 20 Hz. ' ) and viscosity modulus (G " ). Within a given frequency range, DQ8 - G + DH's G ' Curve above DQ8 - G + DH G " These results are due to the transformation of DQ8-G from gel state to sol state after adsorption of DH.

[0023] 4. Fluorescence properties of 8-QP and detection of hydrazine hydrate

[0024] Figure 7 DMSO-H2O (C 8-QP =2×10 -4 M, V DMSO : V 水 = 8:2) solution, 26 equivalents of hydrazine hydrate were added, and the fluorescence of 8-QP was observed to turn on.

[0025] Figure 8 This is a fluorescence titration diagram of adding hydrazine hydrate to a DMSO-H2O solution of the functional molecule 8-QP of the present invention. Fig. 9 is the minimum fluorescence detection limit. As shown in the figure, the minimum fluorescence detection limit of hydrazine hydrate is 6.78×10 -7 M, can detect hydrazine hydrate in aqueous solution with high sensitivity.

[0026] Fig.10 The solid-state fluorescence spectra (λ) of the functional molecule 8-QP of the present invention before and after exposure to different hydrazine hydrate (DH) analog vapors ex =350 nm). 8-QP at λ em = 567 nm. When 8-QP crystal powder was exposed to ethylenediamine and trimethylamine vapor, the em= 567 nm, the yellow fluorescence is quenched, which is caused by the deprotonation process. However, when placed in hydrazine hydrate vapor, the emission color of the crystalline powder changes from yellow to black, which is visible to the naked eye. While the other three groups have almost the same fluorescence emission (≈567 nm), hydrazine hydrate vapor shows a significant blue shift (to 397 nm). This phenomenon may be caused by the synergistic effect of hydrazine hydrate forming multiple hydrogen bonds and deprotonation, resulting in a blue shift in fluorescence.

[0027] 5. Detection Mechanism Analysis

[0028] Fig.11 The functional molecule 8-QP of the present invention was theoretically calculated by Gaussian 09 after adding hydrazine hydrate. Density functional theory (DFT) was used to optimize at the B3LYP-D3 / 6-311G* (d, p) level to obtain the structural views of 8-QP, hydrazine hydrate and 8-QP+hydrazine hydrate. Combined with the ESP electrostatic view ( Fig.11 a) Non-covalent interaction (NCI) diagram ( Fig.11 b), the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) ( Fig.11 c) The analysis revealed the existence of a "synergistic effect" and multiple hydrogen bonds, which strengthened the interaction between the host and the guest.

[0029] Fig.12 This is the NMR titration diagram of the functional molecule 8-QP of the present invention and different equivalents of hydrazine hydrate (DH). When 2.0 equivalents (gradually added) of hydrazine hydrate are added to the 8-QP solution (14 mM). Among them, b, c, d, e, and f correspond to the addition of 0.2, 0.5, 1, 1.5, and 2 equivalents of hydrazine hydrate, respectively, a corresponds to the 8-QP main body and f corresponds to the hydrazine hydrate guest. The H1 resonance of hydrazine hydrate shows a downfield shift, and the H2 signal on 8-QP disappears. This result shows that there is an NH⋯N hydrogen bond between 8-QP and hydrazine hydrate. Due to the formation of NH⋯O hydrogen bond between the oxygen on 8-hydroxyquinoline and hydrazine hydrate, the H3 signal shows an upfield shift. In addition, the H a-f The signal shifts upfield, indicating that the N atom on the quinoline ring forms an intermolecular hydrogen bond with hydrazine, resulting in the upfield shift of the adjacent proton signal peak. g-m The signal peak disappears, indicating that the CH⋯O hydrogen bond interaction between the naphthalene rings is involved in the detection process.

[0030] Fig.13 The infrared spectra of the functional molecule 8-QP and 8-QP after reacting with hydrazine hydrate (DH) vapor are shown in Figure 1. The -NH stretching vibration absorption peak of the functional molecule 8-QP appears at 3378 cm -1 The -C=O contraction vibration absorption peak appears at 1695 cm -1The -C=C contraction vibration absorption peak appears at 1607 cm -1 After adding hydrazine hydrate to 8-QP, the -NH stretching vibration absorption peak shifted to 3348 cm -1 , the -C=O stretching vibration absorption peak shifted to 1670 cm -1 , the -C=C stretching vibration absorption peak shifted to 1598 cm -1 , indicating that there is a significant hydrogen bonding interaction between 8-QP and hydrazine hydrate molecules.

[0031] Fig.14 (a) is the X-ray powder diffraction pattern of the functional molecule 8-QP crystal before and after the reaction with hydrazine hydrate (DH) vapor, and (b) is the X-ray powder diffraction pattern of the functional molecule 8-QP dry gel powder and crystal powder before and after the reaction with hydrazine hydrate (DH) vapor. All samples of the functional molecule 8-QP have new characteristic peaks near 2θ = 27.8°, 27.9° and 28.4°, corresponding to d spacings of 3.19Å, 3.18Å and 3.14Å, respectively. This indicates that there are multiple intermolecular hydrogen bonds in the adsorption process of hydrazine hydrate by 8-QP, resulting in lattice distortion and exposure of new crystal planes. However, the color and fluorescence of the 8-QP crystal after absorbing hydrazine hydrate can be reversibly converted into the color and fluorescence of the original 8-QP crystal by heating desorption, which further indicates that 8-QP can be used as a recycling material for adsorbing and separating hydrazine hydrate.

[0032] In summary, the present invention designs and synthesizes a bisquinoline functionalized naphthalimide derivative (8-QP), which can detect and adsorb and separate hydrazine hydrate vapor through multi-channel through the synergistic effect of quinoline and naphthalimide functional groups. The crystals formed by 8-QP can detect hydrazine hydrate vapor with high selectivity, and the crystals have good adsorption and separation properties for hydrazine hydrate vapor. 8-QP can also form supramolecular organic gels in binary solutions of dimethyl sulfoxide and water, and the 8-QP gel can achieve multi-channel detection of hydrazine hydrate vapor. 8-QP can also detect hydrazine hydrate by fluorescence in DMSO-H2O solution. The addition of hydrazine hydrate can make 8-QP produce yellow-green fluorescence from no fluorescence. The minimum detection limit of 8-QP for hydrazine hydrate in aqueous solution is 6.78×10 -7M. The recognition and detection mechanism of 8-QP for hydrazine hydrate is that the "synergistic effect" of the quinoline and naphthalimide functional groups on the 8-QP body forms multiple intermolecular hydrogen bonds with hydrazine hydrate. Quinoline and naphthalimide are good fluorescent groups that can provide fluorescence and colorimetric signals for the detection and adsorption of hydrazine hydrate. These two functional groups form hydrogen bonds with hydrazine hydrate, causing intermolecular charge transfer, thereby producing corresponding fluorescence changes. At the same time, quinoline and naphthalimide are aromatic ring structures that can provide π···π self-assembly binding sites, which are conducive to the formation of supramolecular gels and crystals. This material has broad application prospects in the detection and adsorption of hydrazine hydrate. BRIEF DESCRIPTION OF THE DRAWINGS

[0033] Figure 1 is the mass spectrum of the functional molecule 8-QP of the present invention;

[0034] Figure 2 is the hydrogen spectrum of the functional molecule 8-QP of the present invention;

[0035] Figure 3 The crystal structure stacking and porosity diagram of the functional molecule 8-QP of the present invention, wherein (a) the structure of 8-QP shows intramolecular hydrogen bonds, (b) the stacking diagram of 8-QP along the crystallographic c-axis, (c) shows the main π···π stacking interactions of 8-QP, and (d) the calculated free volume area in the unit cell of the 8-QP single crystal;

[0036] Figure 4 (a) The functional molecule 8-QP crystal of the present invention is exposed to hydrazine hydrate vapor and different hydrazine hydrate analog vapors for identification and (b) the color change of the crystal before and after adsorption and the recycling performance;

[0037] Figure 5 This is a diagram showing the color and state changes of the supramolecular gel prepared using the functional molecule 8-QP of the present invention before and after the action of hydrazine hydrate (DH) vapor;

[0038] Figure 6 (a) EI, (b) SLB, (c) MSD, (d) G' and G" curves of the supramolecular gel prepared by using the functional molecule 8-QP of the present invention before and after the action of hydrazine hydrate (DH) vapor;

[0039] Figure 7 The fluorescence spectrum (λ) of the functional molecule 8-QP (0.2 mM) of the present invention in DMSO-H2O (8:2, v / v) solution with 26 times the equivalent of hydrazine hydrate (DH) added ex =310 nm);

[0040] Figure 8This is a fluorescence titration diagram of the functional molecule 8-QP (0.2 mM) of the present invention against hydrazine hydrate in a DMSO-H2O (8:2, v / v) solution;

[0041] Fig. 9 The minimum fluorescence detection limit of adding hydrazine hydrate (DH) to the DMSO-H2O solution of the functional molecule 8-QP of the present invention;

[0042] Fig.10 The solid-state fluorescence spectra (λ) of the functional molecule 8-QP of the present invention before and after exposure to different hydrazine hydrate (DH) analog vapors ex =350 nm);

[0043] Fig.11 The Gaussian theory calculation diagrams of the functional molecule 8-QP, hydrazine hydrate (DH), and the interaction between 8-QP and hydrazine hydrate (DH) of the present invention, wherein (a) ESP diagrams of 8-QP and 8-QP + DH, (b) NCI diagram of 8-QP + DH, (c) frontier molecular orbitals (HOMO and LUMO) of 8-QP and 8-QP + DH;

[0044] Fig.12 It is the NMR titration diagram of the functional molecule 8-QP of the present invention and different equivalents of hydrazine hydrate (DH);

[0045] Fig.13 The functional molecule 8-QP of the present invention and the infrared image of 8-QP after reacting with hydrazine hydrate (DH) vapor;

[0046] Fig.14 (a) is the X-ray powder diffraction pattern of the functional molecule 8-QP crystal before and after the reaction with hydrazine hydrate (DH) vapor, and (b) is the X-ray powder diffraction pattern of the functional molecule 8-QP dry gel powder and crystal powder before and after the reaction with hydrazine hydrate (DH) vapor. DETAILED DESCRIPTION

[0047] The synthesis of the functional molecule 8-QP of the present invention and its application in the detection and adsorption separation of hydrazine hydrate vapor are further described below by means of specific examples.

[0048] Example 1 Synthesis of 8-QP

[0049] Under N2 atmosphere, 1,4,5,8-naphthalenetetracarboxylic anhydride (1.45 g, 1.5 mmol) and 2-(quinoline-8-oxy)acetylhydrazine (0.9 g, 0.75 mmol) were added to anhydrous DMF (10 mL) solution and dissolved by stirring at 140°C. The solution was then vigorously stirred at 140°C for 18 h under continuous reflux, then cooled to room temperature, the precipitate was collected by filtration, washed with anhydrous methanol, and finally dried in vacuo at 60°C to obtain a solid yellow powder, which was the target product 8-QP. The yield was 80%. The mass spectrum and hydrogen spectrum of 8-QP are shown in Figure 1 and Figure 2 .

[0050] Example 2 Recognition of hydrazine hydrate by 8-QP supramolecular crystals

[0051] When the 8-QP crystalline powder is exposed to the vapors of hydrazine hydrate, ethanolamine, ammonia water, cyclohexylamine, 2-n-butylamine, ethylenediamine, 1,6-hexanediamine, triethylamine, and trimethylamine, if the color of the 8-QP crystalline powder changes from dark orange to black, it indicates that it is hydrazine hydrate vapor; if the color of the 8-QP crystalline powder cannot change from orange to black, it is other vapors.

[0052] Example 3 Preparation and Detection of Hydrazine Hydrate by 8-QP Supramolecular Organogel

[0053] Preparation of 8-QP supramolecular organogel: 10 mg 8-QP was added to 1 mL DMSO-H2O (8: 2, v / v) binary system, heated in the range of 100-150 °C until 8-QP was completely dissolved, and cooled to room temperature to form a uniform and stable supramolecular organogel.

[0054] When the supramolecular organogel is exposed to hydrazine hydrate vapor, the gel color changes from yellow to black, the fluorescence is quenched, and the gel state is transformed into a sol state. This process is irreversible. Through these changes in gel color, fluorescence, and state, multi-channel detection of hydrazine hydrate vapor by 8-QP gel is achieved.

[0055] Example 4 8-QP Fluorescence Detection of Hydrazine Hydrate

[0056] Pipette 0.5 mL of DMSO-H2O solution of smart supramolecular material 8-QP (C 8-QP =2×10 -4 M, V DMSO : V 水 = 8:2) in a test tube, add 0.06M hydrazine hydrate aqueous solution. The addition of hydrazine hydrate can make 8-QP change from no fluorescence to yellow-green fluorescence. The minimum detection limit of 8-QP for hydrazine hydrate in aqueous solution is 6.78×10 -7 M.

Claims

1. A bisquinoline functionalized naphthalene diimide derivative, the structural formula of which is: 。 2. The method for preparing a bisquinoline functionalized naphthalene diimide derivative as claimed in claim 1, wherein 1,4,5,8-naphthalenetetracarboxylic anhydride and 2-(quinoline-8-oxy)acetohydrazide are added to anhydrous DMF under N2 gas conditions, and the mixture is stirred and dissolved at 135-145°C, and the solution is then vigorously stirred at 135-145°C for 15-20 h under continuous reflux conditions, cooled to room temperature, and the precipitate is collected by filtration, washed with anhydrous methanol, and finally dried in vacuo to obtain the target product, a bisquinoline functionalized naphthalene diimide derivative.

3. The method for preparing the bisquinoline functionalized naphthalimide derivative according to claim 2, characterized in that: The molar ratio of 1,4,5,8-naphthalenetetracarboxylic anhydride to 2-(quinoline-8-oxy)acetohydrazide is 2:

1.

4. Use of the bisquinoline functionalized naphthalimide derivative according to claim 1 in colorimetric identification of hydrazine hydrate vapor.

5. Use of the bisquinoline functionalized naphthalimide derivative according to claim 1 in colorimetric identification of hydrazine hydrate vapor, characterized in that: The functional molecule bisquinoline functionalized naphthalene diimide derivative is slowly evaporated in dimethyl sulfoxide at room temperature to obtain dark orange crystals; when the bisquinoline functionalized naphthalene diimide derivative crystal powder is exposed to hydrazine hydrate, ethanolamine, ammonia water, cyclohexylamine, 2-n-butylamine, ethylenediamine, 1,6-hexanediamine, triethylamine or trimethylamine vapor, only hydrazine hydrate vapor can change the color of the bisquinoline functionalized naphthalene diimide derivative crystal powder from orange to black.

6. Use of the bisquinoline functionalized naphthalimide derivative according to claim 1 in the adsorption separation of hydrazine hydrate.

7. A method for preparing a supramolecular organogel of a bisquinoline functionalized naphthalimide derivative, comprising adding the bisquinoline functionalized naphthalimide derivative described in claim 1 to a DMSO-H2O binary system, heating at 100-150°C until the bisquinoline functionalized naphthalimide derivative is completely dissolved, and cooling to room temperature to form a uniform and stable supramolecular organogel of the bisquinoline functionalized naphthalimide derivative; in the DMSO-H2O binary system, the volume ratio of DMSO to H2O is 8:

2.

8. Use of the bisquinoline functionalized naphthalimide derivative supramolecular organogel prepared by the method as claimed in claim 7 in detecting hydrazine hydrate vapor.

9. Use of the bisquinoline functionalized naphthalimide derivative supramolecular organogel according to claim 8 in detecting hydrazine hydrate vapor, characterized in that: When the bisquinoline-functionalized naphthalene diimide derivative supramolecular organogel was exposed to hydrazine hydrate vapor, the gel color changed from yellow to black, the fluorescence was quenched, and it was transformed from a gel state to a sol state.

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