Virtual template polycyclic aromatic hydrocarbon molecular imprinting material and its preparation method and application

Abstract

The present invention provides a virtual template polycyclic aromatic hydrocarbon molecular imprinting material and its preparation method and application, first, using a molecule with a similar structure to polycyclic aromatic hydrocarbons as a virtual template, the virtual template molecule is selected from 2,3-naphthalene diol, 2-phenanthranol, 9-anthracene alcohol or one or more deuterated pyrene, polycyclic aromatic hydrocarbons are selected from naphthalene, phenanthrene, anthracene or pyrene. One or more, can imprint polycyclic aromatic hydrocarbons that are not suitable as template molecules, thereby expanding the application range of molecular imprinting technology. Secondly, the synthesized virtual template polycyclic aromatic hydrocarbon molecular imprinting polymer is used to adsorb polycyclic aromatic hydrocarbons, and has a very high selective adsorption effect on polycyclic aromatic hydrocarbons, and has a high adsorption capacity. The preparation method of the present invention is simple and reliable, has low cost, is strong in resistance to environmental matrix interference, and has broad application prospects in water pollution remediation.

Description

Technical Field

[0001] The present invention belongs to the technical field of water pollution remediation applications, and in particular relates to a virtual template polycyclic aromatic hydrocarbon molecular imprinting material and a preparation method and application thereof. Background Art

[0002] PAHs have the triple effects of carcinogenicity, teratogenicity and mutagenicity on organisms, and are semi-volatile, easily accumulative and difficult to degrade. Therefore, once they enter the environment, they will cause permanent harm to the entire ecological environment. PAHs will migrate in the environmental medium, and due to their strong fat-soluble characteristics, environmental media rich in organic matter are more likely to become their enrichment points. Therefore, soil will become the destination of PAHs in the environment. PAHs will migrate downward under gravity or groundwater level fluctuations, slowly dissolving into groundwater, leading to long-term groundwater pollution. Groundwater is the most important water source in the world, and about one-third of the population needs to directly rely on drinking water from groundwater. The presence of PAHs pollution in groundwater can induce the occurrence of various human cancers, greatly affecting human health.

[0003] Adsorption is one of the green methods for removing PAHs from water. It removes PAHs through the adsorption activity of adsorbents. This method has the advantages of great adaptability to changes in water quality, easy operation, and low secondary pollution. However, the complex matrix in natural water bodies usually interferes with the adsorption and removal effect of PAHs. Molecular imprinting technology can selectively adsorb PAHs from water environments and is an effective method to improve the removal efficiency of PAHs. PAHs are highly lipophilic compounds with no functional groups (no side chains) in their structure. Imprinting PAHs seems challenging due to the absence of non-covalent interactions such as dipoles, hydrogen bonds, or ionic interactions between PAHs and monomers. Summary of the Invention

[0004] In view of the deficiencies in the prior art, the present invention aims to provide a virtual template polycyclic aromatic hydrocarbon molecular imprinting material and a preparation method and application thereof.

[0005] To achieve the above object, the solution of the present invention is:

[0006] A method for preparing a virtual template polycyclic aromatic hydrocarbon molecularly imprinted material comprises: firstly, using a molecule having a structure similar to that of polycyclic aromatic hydrocarbons as a virtual template; secondly, synthesizing a virtual template polycyclic aromatic hydrocarbon molecularly imprinted polymer, which comprises the following steps:

[0007] (1) Add 0.1-2 mmol of virtual template molecule (preferably 0.5-1 mmol), 10-40 mmol of ethylene glycol dimethacrylate (preferably 15-30 mmol), 2-8 mmol of methacrylic acid (preferably 4-6 mmol) and 0.05-0.3 g of azobisisobutyronitrile (preferably 0.05-0.15 g) to 50-150 mL of acetonitrile (preferably 75-125 mL), perform ultrasonic dispersion, heat in a water bath, and then magnetically stir. After the reaction, filter;

[0008] (2) The above material was placed in a Soxhlet extractor, eluted with 10% by volume acetic acid methanol solution, and then vacuum dried to obtain a virtual template polycyclic aromatic hydrocarbon molecular imprinting material.

[0009] Furthermore, in step (1), the virtual template molecule is selected from one or more of 2,3-naphthalenediol, 2-phenanthranol, 9-anthryl alcohol, or deuterated pyrene. The present invention uses molecules with similar structures to polycyclic aromatic hydrocarbons as virtual templates to enhance the imprinting factor, thereby improving the selective adsorption effect of polycyclic aromatic hydrocarbons in water.

[0010] Furthermore, in step (1), the polycyclic aromatic hydrocarbons are selected from one or more of naphthalene, phenanthrene, anthracene or pyrene.

[0011] Furthermore, in step (1), the ultrasonic dispersion time can be 10-30 min, preferably 10 min.

[0012] Furthermore, in step (1), the temperature of the water bath heating can be 60-80°C, preferably 75°C.

[0013] Furthermore, in step (1), the rotation speed of the magnetic stirring can be 500-800 rpm, preferably 650 rpm.

[0014] Furthermore, in step (1), the reaction time can be 24-36 hours, preferably 28 hours.

[0015] Furthermore, in step (2), the elution time can be 12-36 hours, preferably 24 hours.

[0016] Furthermore, in step (2), the vacuum drying temperature can be 50-70°C, preferably 60°C; and the time can be 24-36h, preferably 36h.

[0017] A virtual template polycyclic aromatic hydrocarbon molecular imprinting material is obtained by the above-mentioned preparation method.

[0018] The virtual template polycyclic aromatic hydrocarbon molecular imprinting material is used to selectively remove polycyclic aromatic hydrocarbons in water.

[0019] Due to the adoption of the above solution, the beneficial effects of the present invention are:

[0020] 1. The present invention uses compounds with similar structures to polycyclic aromatic hydrocarbons as virtual templates, which can imprint polycyclic aromatic hydrocarbons that are not suitable as template molecules, thereby expanding the application scope of molecular imprinting technology.

[0021] 2. Using virtual templates can reduce the cost and difficulty of the experiment and improve the safety of the experiment.

[0022] 3. The polycyclic aromatic hydrocarbon molecular imprinting prepared by the present invention has a strong selective adsorption function, can specifically selectively adsorb polycyclic aromatic hydrocarbons, resist the interference of the water environment matrix, and improve the removal rate of polycyclic aromatic hydrocarbons. It has broad application prospects in water pollution remediation. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] Figure 1 This is a comparison chart of the adsorption effects of naphthalene, carbamazepine and quinoline in a mixed pollutant solution by the virtual template polycyclic aromatic hydrocarbon molecular imprinting materials in Examples 1 to 3. DETAILED DESCRIPTION

[0024] The technical solution of the present invention is further described in detail below in conjunction with several embodiments. This embodiment is implemented on the premise of the technical solution of the invention, and provides a detailed implementation method and specific operation process, but the protection scope of the present invention is not limited to the following embodiments.

[0025] Unless otherwise specified, the experimental materials used in the following examples can be purchased from conventional biochemical reagent companies.

[0026] The present invention will be further described below with reference to the accompanying drawings and specific embodiments, but the present invention is not limited thereto.

[0027] Example 1:

[0028] (1) Selection of PAHs:

[0029] In this example, naphthalene having two benzene rings is selected as the template.

[0030] (2) Selection of virtual template:

[0031] In this embodiment, 2,3-naphthalene diol, which has a similar structure to naphthalene, is selected as the virtual template because naphthalene diol contains two hydroxyl groups, which can enhance the interaction between the virtual template and the functional monomer and improve the imprinting factor.

[0032] (3) Synthesis of virtual template polycyclic aromatic hydrocarbon molecular imprinting materials:

[0033] In this example, 2 mmol of 2,3-naphthalene diol, 10 mmol of ethylene glycol dimethacrylate, 8 mmol of methacrylic acid, and 0.15 g of azobisisobutyronitrile were added to 100 mL of acetonitrile and ultrasonically dispersed for 10 minutes. The mixture was heated in a 75°C water bath with a magnetic stirrer at 650 rpm. After 28 hours of reaction, the mixture was filtered and the virtual template polycyclic aromatic hydrocarbon molecularly imprinted material was placed in a Soxhlet extractor. The template was eluted with 10% (v / v) acetic acid in methanol for 24 hours. After elution, the mixture was vacuum dried at 60°C for 36 hours.

[0034] (4) Preparation of mixed pollutant solution:

[0035] In the embodiment, a 20 mg / L mixed contaminated solution of naphthalene, carbamazepine and quinoline was prepared.

[0036] (5) The specific reaction process is implemented as follows:

[0037] 0.01 g of the virtual template PAH molecularly imprinted material was added to a 20 mg / L contaminated solution of naphthalene, carbamazepine, and quinoline (to a total volume of 100 mL). The solution was then shaken at 200 rpm and 25°C in a magnetic stirrer. After 120 minutes of adsorption, 1 mL of the reaction solution was sampled and the amount of naphthalene adsorbed was determined by high-performance liquid chromatography.

[0038] like Figure 1 As shown, in Example 1, the adsorption capacity of the virtual template polycyclic aromatic hydrocarbon molecularly imprinted material for naphthalene is 98.77 mg / g.

[0039] Example 2:

[0040] Compared with Example 1, the only difference is that the adsorption amount of carbamazepine is detected by high performance liquid chromatography.

[0041] like Figure 1 As shown, in Example 2, the adsorption capacity of carbamazepine by the virtual template polycyclic aromatic hydrocarbon molecular imprinting material is 1.23 mg / g.

[0042] Example 3:

[0043] Compared with Example 1, the only difference is that the adsorption amount of quinoline is detected by high performance liquid chromatography.

[0044] like Figure 1 As shown, in Example 3, the adsorption capacity of quinoline by the virtual template polycyclic aromatic hydrocarbon molecularly imprinted material is 4.76 mg / g.

[0045] Compared with Example 2 and Example 3, the virtual template polycyclic aromatic hydrocarbon molecular imprinting material has the highest adsorption capacity for naphthalene in the mixed pollutant solution (naphthalene = 98.77 mg / g > quinoline = 4.76 mg / g > carbamazepine = 1.23 mg / g), reflecting the selective adsorption ability in mixed pollutants.

[0046] The above description of the embodiments is intended to facilitate understanding and use of the present invention by those skilled in the art. Obviously, the described embodiments are only a portion of the embodiments of the present invention, not all of them. All other embodiments derived by those skilled in the art based on the embodiments of the present invention without inventive effort are also within the scope of protection of the present invention.

Claims

1. A method for preparing a virtual template polycyclic aromatic hydrocarbon molecularly imprinted material, characterized in that: It includes the following steps: (1) Add the virtual template molecule, ethylene glycol dimethacrylate, methacrylic acid and azobisisobutyronitrile into acetonitrile, disperse by ultrasonication, heat in a water bath, and then stir magnetically. After the reaction, filter; (2) Elution with acetic acid methanol solution and vacuum drying to obtain virtual template polycyclic aromatic hydrocarbon molecular imprinting material; In step (1), the virtual template molecule has a structure similar to that of polycyclic aromatic hydrocarbons; In step (1), the virtual template molecule is selected from one or more of 2,3-naphthalene diol, 2-phenanthranol, and 9-anthryl alcohol; In step (1), the polycyclic aromatic hydrocarbons are selected from one or more of naphthalene, phenanthrene, and anthracene.

2. The preparation method according to claim 1, characterized in that In step (1), the ultrasonic dispersion time is 10-30 min.

3. The preparation method according to claim 1, characterized in that In step (1), the water bath heating temperature is 60-80°C.

4. The preparation method according to claim 1, characterized in that In step (1), the rotation speed of the magnetic stirring is 500-800 rpm.

5. The preparation method according to claim 1, characterized in that In step (1), the reaction time is 24-36 hours.

6. The preparation method according to claim 1, characterized in that In step (2), the elution time is 12-36 hours.

7. The preparation method according to claim 1, characterized in that In step (2), the vacuum drying temperature is 50-70°C and the time is 24-36 h.

8. A virtual template polycyclic aromatic hydrocarbon molecular imprinting material, characterized in that The compound is obtained by the preparation method according to any one of claims 1 to 7.

9. A virtual template polycyclic aromatic hydrocarbon molecular imprinting material as claimed in claim 8 for selectively removing polycyclic aromatic hydrocarbons in water.

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