SiO2 solid-phase extraction packing material modified with anthracene-based polyarylene dendritic small molecule gelling factor and its preparation method

Abstract

The application discloses a SiO2 solid-phase extraction filler based on anthracene core polyarylether dendritic micellar gel factor and a preparation method thereof. A dendritic micellar gel agent with anthracene as a core and polyarylether as dendritic is prepared first, and then the dendritic micellar gel agent is chemically bonded with amino silica gel through cyanuric chloride to obtain the solid-phase extraction filler. The obtained filler takes silica gel as a matrix and takes the dendritic micellar gel factor as a surface modifier, and the gel factor contains polyarylether and anthracene units. The dendritic micellar gel factor contains various hydrophilic and hydrophobic groups, can simultaneously provide various interaction forces such as pi-pi stacking, van der Waals force and hydrogen bond, and can improve the adsorption capacity and molecular shape selectivity of the solid-phase extraction filler to organic matters. The filler simultaneously has the advantages of SiO2 and the dendritic micellar gel factor, is suitable for enrichment and separation of trace organic pollutants in environmental water bodies and food, and can improve the accuracy and sensitivity of analyte detection.

Description

Technical Field

[0001] This invention relates to the field of solid-phase extraction technology, and more specifically, to a method for preparing SiO2 solid-phase extraction packing material modified with anthracene nucleus polyarylene ether dendritic small molecule gel factor. Background Technology

[0002] Solid-phase extraction (SPE) is a commonly used sample pretreatment method widely applied in environmental science, food science, and biomedicine. The basic principle of SPE is to selectively adsorb organic pollutants in a sample using a solid-phase adsorbent, thereby achieving the separation and enrichment of these pollutants. However, SPE also has limitations, the most significant being the issue of molecular shape recognition. The adsorption process in SPE primarily relies on intermolecular forces, such as van der Waals forces, hydrogen bonds, and hydrophobicity. These forces are closely related to factors such as molecular shape, size, and charge; therefore, SPE's ability to recognize molecular shapes is significantly limited. For example, SPE may be unable to distinguish molecules with similar shapes. To overcome the limitations of SPE in molecular shape recognition, researchers have developed solid-phase adsorbents with higher recognition capabilities, such as molecularly imprinted materials. Newly discovered SPE adsorbents, compared to traditional SPE adsorbents, possess advantages such as large specific surface area, good adsorption selectivity, strong adsorption capacity, large adsorption capacity, and high reusability. These mainly include magnetic nanomaterials, metal nanomaterials, carbon nanomaterials, and biomaterials. Magnetic solid-phase extraction (SPE) is a solid-phase extraction technique that uses magnetic or magnetizable materials as adsorbent matrices. Because magnetic adsorbents can rapidly aggregate under an external magnetic field, the target analyte completes the adsorption and elution process in a short time, significantly shortening the extraction time. Metal oxide nanoparticles possess advantages such as stable physicochemical properties, large surface area, and simple preparation methods, and can be used as modifying materials loaded onto certain matrices for SPE adsorbents. The chemical and physical properties of metal-organic frameworks can be appropriately modified through ligand design, exhibiting characteristics such as large surface area and finely tunable porosity, which can improve the adsorption efficiency of target pollutants when used as SPE packing materials. Graphene, a novel carbonaceous material with a two-dimensional lattice structure, possesses a large specific surface area, excellent thermal and chemical stability, and ultra-high mechanical strength, showing promising potential for application as an SPE adsorbent.

[0003] Despite this, silicon-based materials remain the most widely used solid-phase extraction matrix materials due to their advantages such as large specific surface area, good biocompatibility, strong mechanical stability, ease of modification, and low cost. Because silicon-based materials lack sufficient binding sites, it is usually necessary to effectively graft various specific inorganic or organic molecules onto their surfaces to achieve high selectivity in the silicon-based adsorbent and thus modify the silicon-based materials. Dendritic molecules are highly branched compounds containing repeating groups. Their unique structure and the presence of various polar and nonpolar functional groups have led to their applications in biomedicine, drug delivery, nanocomposites, and supramolecular materials. Since their first report in 1987, organic small molecule gels have become a remarkable type of soft material due to their unique structure. Dendritic gel molecules with special structures not only possess the ability to "programmably" control molecular "information" like general gel small molecules, but also have a structure similar to the repeating units in polymer gels, allowing for regulation and construction through multiple non-covalent interactions during self-assembly. Based on this, this patent utilizes dendritic molecules to construct small molecule gel factors to modify silica, thereby improving its adsorption selectivity and molecular recognition ability. Summary of the Invention

[0004] The technical problem to be solved by this invention is to provide a SiO2 solid-phase extraction packing material modified with anthracene-core polyarylene ether dendritic small molecule gel factor and its preparation method. Using silica microspheres as the matrix, dendritic small molecule gel factors with anthracene core and polyarylene ether as dendrites are bonded to the SiO2 surface by cyanuric chloride as a solid-phase extraction packing material. This solid-phase extraction packing material combines the advantages of dendritic small molecule gel and silica microspheres. When filled into a solid-phase extraction column for sample pretreatment, it can enrich polycyclic aromatic hydrocarbons.

[0005] This invention provides a SiO2 solid-phase extraction packing material modified with anthracene-based polyarylene ether dendritic small molecule gelling agent. The solid-phase extraction packing material uses amino silica gel as a matrix, and the dendritic small molecule gelling agent is bonded to the surface of the amino silica gel via a Friedel-Crafts reaction of cyanuric chloride and the gelling agent, thus constructing a silica solid-phase extraction material modified with a dendritic small molecule gelling agent. The surface of this solid-phase extraction material contains polyarylene ether and anthracene groups, and its structural formula is as follows:

[0006]

[0007] This invention also provides a method for preparing SiO2 solid-phase extraction packing material modified with anthracene nucleus polyarylene ether dendritic small molecule gelling factor, comprising the following steps:

[0008] (1) Preparation of G1-COOCH3: Methyl 3,4,5-trihydroxybenzoate and anhydrous potassium carbonate were dissolved in 1,4-dioxane to obtain a first mixture. Benzyl chloride was added to the first mixture and mixed well, followed by the addition of tert-butylammonium iodide and mixed well. The mixture was then reacted at 100-120℃ for 20-36 h. After the reaction was completed, the solvent was removed by rotary evaporation to obtain an oily substance. The oily substance was recrystallized in methanol at 55-85℃ to obtain white needle-like crystals of G1-COOCH3.

[0009] (2) Preparation of G1-CONHNH2: Anhydrous methanol and tetrahydrofuran were mixed to obtain a second mixture. G1-COOCH3 obtained in step (1) and hydrazine hydrate were mixed to obtain a suspension. The suspension was slowly added dropwise to the second mixture and mixed evenly. Then it was reacted at 65-75℃ for 10-24h. After the reaction was completed, the solvent was removed by rotary evaporation. The solid obtained after rotary evaporation was dissolved in dichloromethane. Deionized water was added to extract the solid. The solvent was evaporated from the organic layer at 45-65℃ to obtain the crude product. The crude product was purified by column chromatography to obtain white powder G1-CONHNH2.

[0010] (3) Preparation of Gpy: 9-anthracene carboxaldehyde was dissolved in methanol solution to obtain a third mixture. G1-CONHNH2 prepared in step (2) was dissolved in chloroform to obtain a fourth mixture. The third mixture was slowly added dropwise to the fourth mixture. The reaction was carried out at 20-27℃ for 12-36h. After the reaction was completed, the solvent was removed by filtration to obtain a crude product. The crude product was recrystallized with dichloromethane at 40-70℃ to obtain a yellow solid product Gpy.

[0011] (4) Preparation of SiO2-Gpy: Add the Gpy prepared in step (3) to anhydrous aluminum chloride to obtain the fifth mixture. Add amino silica gel and cyanuric chloride to anhydrous dichloromethane to obtain the sixth mixture. Heat and stir the sixth mixture in an oil bath at 40-60℃ for 30-60 min. After the reaction is completed, cool to room temperature and then add the fifth mixture. Then heat and stir in an oil bath at 40-60℃ for 12-24 h. After the reaction is completed, wash three times each with dichloromethane, methanol and water. After centrifugation for 3 min, dry at 100-150℃ for 12-36 h to obtain the silica-dendritic molecular gel composite material SiO2-Gpy.

[0012] Preferably, the addition ratio of each raw material is as follows:

[0013] The addition ratio of each raw material in step (1) is methyl 3,4,5-trihydroxybenzoate: anhydrous potassium carbonate: 1,4-dioxane: benzyl chloride: tert-butylammonium iodide = (8-11)g: (23-26)g: (120-150)mL: (32-35)mL: (1.3-1.7)g;

[0014] The addition ratio of each raw material in step (2) is G1-COOCH3: hydrazine hydrate: anhydrous methanol: tetrahydrofuran: dichloromethane = (3-7)g: (18-24)mL: (28-34)mL: (12-17)mL: (50-100)mL;

[0015] The addition ratio of each raw material in step (3) is 9-anthracene formaldehyde: methanol: G1-CONHNH2: chloroform: dichloromethane: = (0.1-0.5)g: (50-80)mL: (0.4-1.0)g: (50-80)mL: (100-200)mL;

[0016] The addition ratio of each raw material in step (4) is as follows: amino silica gel: cyanuric chloride: anhydrous dichloromethane: Gpy: anhydrous aluminum chloride = (2.0-6.0)g: (0.2-0.6)g: (80-120)mL: (0.2-0.6)g: (0.4-0.6)g.

[0017] Preferably, the addition ratio of each raw material in step (1) is methyl 3,4,5-trihydroxybenzoate: anhydrous potassium carbonate: 1,4-dioxane: benzyl chloride: tert-butylammonium iodide = 9.0015g: 24.8457g: 130mL: 33mL: 1.4003g; the reaction temperature is 110℃, the reaction time is 24h, and the recrystallization temperature is 75℃.

[0018] Preferably, the addition ratio of each raw material in step (2) is G1-COOCH3: hydrazine hydrate: anhydrous methanol: tetrahydrofuran: dichloromethane = 4.0028g: 22mL: 30mL: 15mL: 100mL; the reaction temperature is 70℃, the reaction time is 12h, and the evaporation temperature is 55℃.

[0019] Preferably, the addition ratio of each raw material in step (3) is 9-anthracene formaldehyde: methanol: G1-CONHNH2: chloroform: dichloromethane: = 0.2315g: 70mL: 0.5030g: 70mL: 200mL.

[0020] Preferably, the addition ratio of each raw material in step (4) is amino silicone: cyanuric chloride: anhydrous dichloromethane: Gpy: anhydrous aluminum chloride = 5.1870g: 0.5230g: 100mL: 0.2032g: 0.4580g.

[0021] Synthesis Principle of this Invention: This invention utilizes a chemical method to bond dendritic small-molecule gel factors to the surface of SiO2 as a solid-phase extraction (SPE) filler. Specifically, the dendritic small-molecule gel factors are bonded to the surface of amino silica gel via a Friedel-Crafts reaction with cyanuric chloride, serving as the SiO2-Gpy SPE filler. Because the synthesized dendritic small-molecule gel factors contain various hydrophilic and hydrophobic groups, they can simultaneously provide multiple interaction forces such as π-π stacking, van der Waals forces, and hydrogen bonds. Bonding them to the SiO2 surface via a chemical method as a SPE filler improves the adsorption capacity and molecular shape selectivity of the SPE filler for organic matter. The filler combines the advantages of both SiO2 and dendritic small-molecule gel factors, making it suitable for the enrichment and separation of trace organic pollutants in environmental water and food, thereby improving the accuracy and sensitivity of analyte detection.

[0022] The beneficial effects of this invention are as follows: The solid-phase extraction (SPE) packing material synthesized in this invention is silica modified with dendritic low-molecular-weight gelling agents based on anthracene core and polyarylene ether dendrites. The highly branched structure of the dendritic small-molecule gelling agent and its abundance of functional groups provide various interaction forces, such as π-π stacking, hydrogen bonding, hydrophobic interactions, and van der Waals forces. By chemically bonding the dendritic small-molecule gelling agents to silica microspheres, the resulting SPE packing material possesses the advantages of both, while reducing the disadvantages of using them alone as SPE packing materials. This special structure can improve the adsorption capacity of the SPE packing material for target analytes, exhibiting good selective adsorption, simple elution operation, and good adsorption capacity and selectivity for five polycyclic aromatic hydrocarbons: anthracene, naphthalene, fluoranthene, pyrene, and diphenylmethane. It is then packed into a solid-phase extraction column for sample pretreatment to enrich polycyclic aromatic hydrocarbons. Attached Figure Description

[0023] Figure 1 The structural diagram of SiO2-Gpy, a SiO2 solid-phase extraction filler modified with anthracene-based polyarylene ether dendritic small molecule gelling factor;

[0024] Figure 2 Infrared characterization of SiO2-Gpy, a SiO2 solid-phase extraction filler modified with anthracene-core polyarylene ether dendritic small molecule gelling factor.

[0025] Figure 3 Nuclear magnetic resonance of Gpy, a dendritic molecular gelling agent 1 H spectrum;

[0026] Figure 4 Thermogravimetric analysis of solid-phase extraction fillers SiO2-Gpy and SiO2-NH2;

[0027] Figure 5 Chromatographic comparison of anthracene before and after adsorption by SiO2-Gpy solid-phase extraction packing material;

[0028] Figure 6 Chromatographic comparison of SiO2-Gpy solid-phase extraction packing material before and after adsorption of pyrene;

[0029] Figure 7 Chromatographic comparison of SiO2-Gpy solid-phase extraction packing material before and after adsorption of naphthalene;

[0030] Figure 8 Chromatographic comparison of SiO2-Gpy solid-phase extraction packing material before and after adsorption of fluoranthene;

[0031] Figure 9 Chromatographic comparison of diphenylmethane before and after adsorption by the SiO2-Gpy solid-phase extraction packing material. Detailed Implementation

[0032] To make the technical solution of the present invention easier to understand, the technical solution of the present invention will now be clearly and completely described in conjunction with the accompanying drawings and specific embodiments.

[0033] Example 1:

[0034] The preparation method of SiO2 solid-phase extraction packing material based on anthracene nucleus polyarylene ether dendritic small molecule gelling factor modified in this embodiment includes the following steps:

[0035] (1) Preparation of G1-COOCH3: Methyl 3,4,5-trihydroxybenzoate and anhydrous potassium carbonate were dissolved in 1,4-dioxane to obtain a first mixture. Benzyl chloride was added to the first mixture and mixed well, followed by the addition of tert-butylammonium iodide and mixed well. The mixture was then reacted at 100-120℃ for 20-36 h. After the reaction was completed, the solvent was removed by rotary evaporation to obtain an oily substance. The oily substance was recrystallized in methanol at 55-85℃ to obtain white needle-like crystals of G1-COOCH3.

[0036] The addition ratio of each raw material is methyl 3,4,5-trihydroxybenzoate: anhydrous potassium carbonate: 1,4-dioxane: benzyl chloride: tert-butylammonium iodide = 9.0015g: 24.8457g: 130mL: 33mL: 1.4003gg;

[0037] (2) Preparation of G1-CONHNH2: Anhydrous methanol and tetrahydrofuran were mixed to obtain a second mixture. G1-COOCH3 obtained in step (1) and hydrazine hydrate were mixed to obtain a suspension. The suspension was slowly added dropwise to the second mixture and mixed evenly. Then it was reacted at 65-75℃ for 10-24h. After the reaction was completed, the solvent was removed by rotary evaporation. The solid obtained after rotary evaporation was dissolved in dichloromethane. Deionized water was added to extract the solid. The solvent was evaporated from the organic layer at 45-65℃ to obtain the crude product. The crude product was purified by column chromatography to obtain white powder G1-CONHNH2.

[0038] The addition ratio of each raw material is G1-COOCH3: hydrazine hydrate: anhydrous methanol: tetrahydrofuran: dichloromethane = 4.0028g: 22mL: 30mL: 15mL: 100mL; the reaction temperature is 70℃, the reaction time is 12h, and the evaporation temperature is 55℃.

[0039] (3) Preparation of Gpy: 9-anthracene carboxaldehyde was dissolved in methanol solution to obtain a third mixture. G1-CONHNH2 prepared in step (2) was dissolved in chloroform to obtain a fourth mixture. The third mixture was slowly added dropwise to the fourth mixture. The reaction was carried out at 20-27℃ for 12-36h. After the reaction was completed, the solvent was removed by filtration to obtain a crude product. The crude product was recrystallized with dichloromethane at 40-70℃ to obtain a yellow solid product Gpy.

[0040] The addition ratio of each raw material is 9-anthracarbaldehyde:methanol:G1-CONHNH2:trichloromethane:dichloromethane:=0.2315g:70mL:0.5030g:70mL:200mL;

[0041] (4) Preparation of SiO2-Gpy: Add the Gpy prepared in step (3) to anhydrous aluminum chloride to obtain the fifth mixture. Add amino silica gel and cyanuric chloride to anhydrous dichloromethane to obtain the sixth mixture. Heat and stir the sixth mixture in an oil bath at 40-60℃ for 30-60 min. After the reaction is completed, cool to room temperature and then add the fifth mixture. Then heat and stir in an oil bath at 40-60℃ for 12-24 h. After the reaction is completed, wash three times with dichloromethane, methanol and water. After centrifugation for 3 min, dry at 100-150℃ for 12-36 h to obtain SiO2-Gpy sample 3 of silica-dendritic molecular gel composite material.

[0042] The proportions of each raw material are as follows: amino silica gel: cyanuric chloride: anhydrous dichloromethane: Gpy: anhydrous aluminum chloride = 5.1870g: 0.5230g: 100mL: 0.2032g: 0.4580g.

[0043] Example 2:

[0044] The preparation method of SiO2 solid-phase extraction packing material based on anthracene nucleus polyarylene ether dendritic small molecule gelling factor modified in this embodiment includes the following steps:

[0045] (1) Preparation of G1-COOCH3: Methyl 3,4,5-trihydroxybenzoate and anhydrous potassium carbonate were dissolved in 1,4-dioxane to obtain a first mixture. Benzyl chloride was added to the first mixture and mixed well, followed by the addition of tert-butylammonium iodide and mixed well. The mixture was then reacted at 100-120℃ for 20-36 h. After the reaction was completed, the solvent was removed by rotary evaporation to obtain an oily substance. The oily substance was recrystallized in methanol at 55-85℃ to obtain white needle-like crystals of G1-COOCH3.

[0046] The addition ratio of each raw material is methyl 3,4,5-trihydroxybenzoate: anhydrous potassium carbonate: 1,4-dioxane: benzyl chloride: tert-butylammonium iodide = 8g: 26g: 120mL: 35mL: 1.3g;

[0047] (2) Preparation of G1-CONHNH2: Anhydrous methanol and tetrahydrofuran were mixed to obtain a second mixture. G1-COOCH3 obtained in step (1) and hydrazine hydrate were mixed to obtain a suspension. The suspension was slowly added dropwise to the second mixture and mixed evenly. Then it was reacted at 65-75℃ for 10-24h. After the reaction was completed, the solvent was removed by rotary evaporation. The solid obtained after rotary evaporation was dissolved in dichloromethane. Deionized water was added to extract the solid. The solvent was evaporated from the organic layer at 45-65℃ to obtain the crude product. The crude product was purified by column chromatography to obtain white powder G1-CONHNH2.

[0048] The addition ratio of each raw material is G1-COOCH3: hydrazine hydrate: anhydrous methanol: tetrahydrofuran: dichloromethane = 3g: 24mL: 28mL: 17mL: 50mL;

[0049] (3) Preparation of Gpy: 9-anthracene carboxaldehyde was dissolved in methanol solution to obtain a third mixture. G1-CONHNH2 prepared in step (2) was dissolved in chloroform to obtain a fourth mixture. The third mixture was slowly added dropwise to the fourth mixture. The reaction was carried out at 20-27℃ for 12-36h. After the reaction was completed, the solvent was removed by filtration to obtain a crude product. The crude product was recrystallized with dichloromethane at 40-70℃ to obtain a yellow solid product Gpy.

[0050] The addition ratio of each raw material is 9-anthracarbaldehyde:methanol:G1-CONHNH2:trichloromethane:dichloromethane:=0.1g:80mL:0.4g:80mL:100mL;

[0051] (4) Preparation of SiO2-Gpy: Add the Gpy prepared in step (3) to anhydrous aluminum chloride to obtain the fifth mixture. Add amino silica gel and cyanuric chloride to anhydrous dichloromethane to obtain the sixth mixture. Heat and stir the sixth mixture in an oil bath at 40-60℃ for 30-60 min. After the reaction is completed, cool to room temperature and then add the fifth mixture. Heat and stir in an oil bath at 40-60℃ for 12-24 h. After the reaction is completed, wash three times with dichloromethane, methanol and water. After centrifugation for 3 min, dry at 100-150℃ for 12-36 h to obtain SiO2-Gpy sample 2 of silica-dendritic molecular gel composite material.

[0052] The addition ratio of each raw material is as follows: amino silicone: cyanuric chloride: anhydrous dichloromethane: Gpy: anhydrous aluminum chloride = 2.0g: 0.6g: 80mL: 0.6g: 0.4g.

[0053] Example 3:

[0054] The preparation method of SiO2 solid-phase extraction packing material based on anthracene nucleus polyarylene ether dendritic small molecule gelling factor modified in this embodiment includes the following steps:

[0055] (1) Preparation of G1-COOCH3: Methyl 3,4,5-trihydroxybenzoate and anhydrous potassium carbonate were dissolved in 1,4-dioxane to obtain a first mixture. Benzyl chloride was added to the first mixture and mixed well, followed by the addition of tert-butylammonium iodide and mixed well. The mixture was then reacted at 100-120℃ for 20-36 h. After the reaction was completed, the solvent was removed by rotary evaporation to obtain an oily substance. The oily substance was recrystallized in methanol at 55-85℃ to obtain white needle-like crystals of G1-COOCH3.

[0056] The addition ratio of each raw material is methyl 3,4,5-trihydroxybenzoate: anhydrous potassium carbonate: 1,4-dioxane: benzyl chloride: tert-butylammonium iodide = 11g: 23g: 150mL: 32mL: 1.7g;

[0057] (2) Preparation of G1-CONHNH2: Anhydrous methanol and tetrahydrofuran were mixed to obtain a second mixture. G1-COOCH3 obtained in step (1) and hydrazine hydrate were mixed to obtain a suspension. The suspension was slowly added dropwise to the second mixture and mixed evenly. Then it was reacted at 65-75℃ for 10-24h. After the reaction was completed, the solvent was removed by rotary evaporation. The solid obtained after rotary evaporation was dissolved in dichloromethane. Deionized water was added to extract the solid. The solvent was evaporated from the organic layer at 45-65℃ to obtain the crude product. The crude product was purified by column chromatography to obtain white powder G1-CONHNH2.

[0058] The addition ratio of each raw material is G1-COOCH3: hydrazine hydrate: anhydrous methanol: tetrahydrofuran: dichloromethane = 7g: 18mL: 34mL: 12mL: 100mL;

[0059] (3) Preparation of Gpy: 9-anthracene carboxaldehyde was dissolved in methanol solution to obtain a third mixture. G1-CONHNH2 prepared in step (2) was dissolved in chloroform to obtain a fourth mixture. The third mixture was slowly added dropwise to the fourth mixture. The reaction was carried out at 20-27℃ for 12-36h. After the reaction was completed, the solvent was removed by filtration to obtain a crude product. The crude product was recrystallized with dichloromethane at 40-70℃ to obtain a yellow solid product Gpy.

[0060] The addition ratio of each raw material is 9-anthracarbaldehyde:methanol:G1-CONHNH2:trichloromethane:dichloromethane:=0.5g:50mL:1.0g:50mL:200mL;

[0061] (4) Preparation of SiO2-Gpy: Add the Gpy prepared in step (3) to anhydrous aluminum chloride to obtain the fifth mixture. Add amino silica gel and cyanuric chloride to anhydrous dichloromethane to obtain the sixth mixture. Heat and stir the sixth mixture in an oil bath at 40-60℃ for 30-60 min. After the reaction is completed, cool to room temperature and then add the fifth mixture. Then heat and stir in an oil bath at 40-60℃ for 12-24 h. After the reaction is completed, wash three times with dichloromethane, methanol and water. After centrifugation for 3 min, dry at 100-150℃ for 12-36 h to obtain SiO2-Gpy sample 3 of silica-dendritic molecular gel composite material.

[0062] The proportions of each raw material are as follows: amino silica gel: cyanuric chloride: anhydrous dichloromethane: Gpy: anhydrous aluminum chloride = 6.0g: 1.2g: 120mL: 0.2g: 0.6g.

[0063] Application example:

[0064] Weigh 0.5 g of the SiO2-Gpy solid-phase extraction (SPE) packing material prepared in the example, and dry-pack it into a 3 mL SPE column. Cover both ends of the column with sintered plates to obtain the SPE column. Activate the SPE column with 5 mL of buffer solution at a flow rate of 1.0 mL / min. Then, transfer 10 mL of the test sample (standard solutions of five polycyclic aromatic hydrocarbons: anthracene, naphthalene, fluoranthene, pyrene, and diphenylmethane) at a concentration of 25 μg / mL into the column at a flow rate of 0.1 mL / min. Finally, elute with 10 mL of dichloromethane at a flow rate of 0.1 mL / min. Collect the eluent, filter it through a 0.22 μm organic filter membrane, and determine the content of the five polycyclic aromatic hydrocarbons by high-performance liquid chromatography (HPLC). The chromatographic conditions were: acetonitrile:water (90 / 10, v / v), flow rate 1.0 mL / min, temperature 40 °C, and detection wavelength 254 nm. The results were obtained by using the formula... Calculate the adsorption capacity of the solid-phase extraction packing material, q e (mg / g) represents the adsorption capacity. and V represents the initial and equilibrium concentrations of the polycyclic aromatic hydrocarbons (PAHs), V (mL) represents the loading volume of the PAHs, and m (mg) represents the mass of the solid-phase extraction packing material.

[0065] Table 1. Elemental proportions of aminosilicone and aminosilicone modified with dendritic small molecule gelling factor Gpy.

[0066] <![CDATA[SiO2-NH2]]> 4.61 1.62 1.60 <![CDATA[SiO2-Gpy]]> 6.49 2.18 2.38

[0067] Table 2 Adsorption capacity of the SiO2-Gpy packing material prepared in this invention for various target analytes

[0068]

[0069] It should be noted that the embodiments described herein are only some embodiments of the present invention, and not all implementations of the present invention. These embodiments are merely illustrative and are intended only to provide a more intuitive and clear way to understand the content of the present invention, not to limit the technical solutions described herein. All other implementation methods that can be conceived by those skilled in the art without creative effort, as well as other simple substitutions and variations of the technical solutions of the present invention, without departing from the concept of the present invention, are within the protection scope of the present invention.

Claims

1. An application of SiO2 modified with anthracene-based polyarylene ether dendritic small molecule gelling factor as a solid-phase extraction filler, characterized in that, The solid-phase extraction packing material uses amino silica gel as a matrix, and is bonded to the surface of amino silica gel via a Friedel-Crafts reaction between cyanuric chloride and dendritic small molecule gelling agents. The dendritic small molecule gelling agents contain polyaryl ether and anthracene units, and their structural formula is as follows: 。 2. The application of SiO2 modified with anthracene nucleus polyarylene ether dendritic small molecule gelling factor as described in claim 1 as a solid-phase extraction filler, characterized in that, The solid-phase extraction packing material is prepared by the following steps: (1) Preparation of G1-COOCH3: Methyl 3,4,5-trihydroxybenzoate and anhydrous potassium carbonate were dissolved in 1,4-dioxane to obtain a first mixture. Benzyl chloride was added to the first mixture and mixed well, followed by the addition of tert-butylammonium iodide and mixed well. The mixture was then reacted at 100-120℃ for 20-36 h. After the reaction was completed, the solvent was removed by rotary evaporation to obtain an oily substance. The oily substance was recrystallized in methanol at 55-85℃ to obtain white needle-like crystals of G1-COOCH3. (2) Preparation of G1-CONHNH2: Anhydrous methanol and tetrahydrofuran were mixed to obtain a second mixture. G1-COOCH3 obtained in step (1) and hydrazine hydrate were mixed to obtain a suspension. The suspension was slowly added dropwise to the second mixture and mixed evenly. Then it was reacted at 65-75℃ for 10-24h. After the reaction was completed, the solvent was removed by rotary evaporation. The solid obtained after rotary evaporation was dissolved in dichloromethane. Deionized water was added to extract the solid. The solvent was evaporated from the organic layer at 45-65℃ to obtain the crude product. The crude product was purified by column chromatography to obtain white powder G1-CONHNH2. (3) Preparation of Gpy: 9-anthracene carboxaldehyde was dissolved in methanol solution to obtain a third mixture. G1-CONHNH2 prepared in step (2) was dissolved in chloroform to obtain a fourth mixture. The third mixture was slowly added dropwise to the fourth mixture. The reaction was carried out at 20-27℃ for 12-36h. After the reaction was completed, the solvent was removed by filtration to obtain a crude product. The crude product was recrystallized with dichloromethane at 40-70℃ to obtain a yellow solid product Gpy. (4) Preparation of SiO2-Gpy: Add the Gpy prepared in step (3) to anhydrous aluminum chloride to obtain the fifth mixture. Add amino silica gel and cyanuric chloride to anhydrous dichloromethane to obtain the sixth mixture. Heat and stir the sixth mixture in an oil bath at 40-60℃ for 30-60 min. After the reaction is completed, cool to room temperature and then add the fifth mixture. Then heat and stir in an oil bath at 40-60℃ for 12-24 h. After the reaction is completed, wash three times each with dichloromethane, methanol and water. After centrifugation for 3 min, dry at 100-150℃ for 12-36 h to obtain the silica-dendritic molecular gel composite material SiO2-Gpy.

3. The application of SiO2 modified with anthracene nucleopolyarylene dendritic small molecule gelling factor as described in claim 2 as a solid-phase extraction filler, characterized in that, The proportions of each ingredient added are as follows: The addition ratio of each raw material in step (1) is methyl 3,4,5-trihydroxybenzoate: anhydrous potassium carbonate: 1,4-dioxane: benzyl chloride: tert-butylammonium iodide = (8-11)g: (23-26)g: (120-150)mL: (32-35)mL: (1.3-1.7)g; The addition ratio of each raw material in step (2) is G1-COOCH3: hydrazine hydrate: anhydrous methanol: tetrahydrofuran: dichloromethane = (3-7)g: (18-24)mL: (28-34)mL: (12-17)mL: (50-100)mL; The addition ratio of each raw material in step (3) is 9-anthracene formaldehyde: methanol: G1-CONHNH2: chloroform: dichloromethane: = (0.1-0.5)g: (50-80)mL: (0.4-1.0)g: (50-80)mL: (100-200)mL; The addition ratio of each raw material in step (4) is as follows: amino silica gel: cyanuric chloride: anhydrous dichloromethane: Gpy: anhydrous aluminum chloride = (2.0-6.0)g: (0.2-0.6)g: (80-120)mL: (0.2-0.6)g: (0.4-0.6)g.

4. The application of SiO2 modified with anthracene nucleopolyarylene dendritic small molecule gelling factor as described in claim 2 as a solid-phase extraction filler, characterized in that, The addition ratio of each raw material in step (1) is methyl 3,4,5-trihydroxybenzoate: anhydrous potassium carbonate: 1,4-dioxane: benzyl chloride: tert-butylammonium iodide = 9.0015g: 24.8457g: 130mL: 33mL: 1.4003g; the reaction temperature is 110℃, the reaction time is 24h, and the recrystallization temperature is 75℃.

5. The application of SiO2 modified with anthracene nucleopolyarylene dendritic small molecule gelling factor as described in claim 2 as a solid-phase extraction filler, characterized in that, The addition ratio of each raw material in step (2) is G1-COOCH3: hydrazine hydrate: anhydrous methanol: tetrahydrofuran: dichloromethane = 4.0028g: 22mL: 30mL: 15mL: 100mL; the reaction temperature is 70℃, the reaction time is 12h, and the evaporation temperature is 55℃.

6. The application of SiO2 modified with anthracene nucleopolyarylene dendritic small molecule gelling factor as described in claim 2 as a solid-phase extraction filler, characterized in that, The addition ratio of each raw material in step (3) is 9-anthracene formaldehyde: methanol: G1-CONHNH2: chloroform: dichloromethane: = 0.2315g: 70mL: 0.5030g: 70mL: 200mL.

7. The application of SiO2 modified with anthracene nucleopolyarylene dendritic small molecule gelling factor as described in claim 2 as a solid-phase extraction filler, characterized in that, The addition ratio of each raw material in step (4) is as follows: amino silicone: cyanuric chloride: anhydrous dichloromethane: Gpy: anhydrous aluminum chloride = 5.1870g: 0.5230g: 100mL: 0.2032g: 0.4580g.

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