CN-121972139-A - Preparation and application of molecular imprinting microporous organic network composite material for selectively enriching ganoderic acid substances

Abstract

The invention discloses synthesis and application of a ganoderic acid molecular imprinting magnetic micropore organic network material for selectively enriching ganoderic acid substances, and belongs to the field of material preparation. The invention prepares the ganoderic acid molecular imprinting magnetic micropore organic network material with large specific surface area, good selectivity and high adsorption capacity by a simple one-pot method. The material contains rich delocalized pi bond, carboxyl, amino and specific hydrogen bond action sites, and can generate stronger hydrogen bond action and pi-pi interaction with ganoderic acid substances containing active sites such as steroid ring, hydroxyl, carbonyl and the like, thereby achieving the enhanced enrichment effect. The material is used as an adsorbent for a magnetic solid-phase extraction method and is used for high-selectivity enrichment and high-sensitivity detection of ganoderic acid substances.

Inventors

• LU QIAOMEI
• ZHANG WENMIN
• HUANG LE
• QIU HAIYANG
• CHEN LI
• ZHANG LAN

Assignees

• 福州大学

Dates

Publication Date

20260505

Application Date

20260202

Claims (10)

1. 1. A preparation method of a molecular imprinting microporous organic network composite material for selectively enriching ganoderic acid substances is characterized by comprising the steps of adding template molecules and functional monomers into a mixed solvent A, adding a magnetic microporous organic network material, uniformly mixing by ultrasound, adding a cross-linking agent and an initiator, fully dispersing in the mixed solvent, heating, washing a product by using an ethanol-acetic acid mixed solution, and drying to obtain a ganoderic acid molecular imprinting microporous organic network material, wherein the mixed solvent A is acetonitrile and N, N-dimethylformamide, and the template molecules, the functional monomers, the cross-linking agent and the initiator are oleanolic acid, methacrylic acid, ethylene glycol dimethacrylate and azodiisobutyronitrile respectively.
2. 2. The preparation method according to claim 1, wherein the volume ratio of ethanol to acetic acid is 9:1, and the volume ratio of acetonitrile to N, N-dimethylformamide in the mixed solvent a is 5:1.
3. 3. The method according to claim 1, wherein the molar ratio of the oleanolic acid, the methacrylic acid, the ethylene glycol dimethacrylate and the azobisisobutyronitrile is 1:4:20:0.2.
4. 4. The method according to claim 1, wherein the ultrasonic time is 2h, the heating condition is 60 ℃ heating 24: 24h, and the drying condition is 60 ℃ drying 6: 6 h.
5. 5. The method of claim 1, wherein the method of preparing the magnetic microporous organic network material comprises: (1) Adding a ferroferric oxide ball, cuprous iodide and bis (triphenylphosphine) palladium dichloride into the mixed solvent B, and performing ultrasonic treatment to obtain a mixed solvent C; (2) Adding halogenated aromatic hydrocarbon monomer and alkyne-containing monomer into the mixed solvent C, heating and stirring, separating by using a magnet, discarding supernatant, washing the obtained product with dichloromethane and methanol for three times respectively, and drying to obtain the magnetic microporous organic network material.
6. 6. The preparation method of claim 5, wherein the mixed solvent B in the step (1) is formed by mixing triethylamine and toluene according to a volume ratio of 1:1, and the mass ratio of the used ferroferric oxide balls to the used cuprous iodide to the bis (triphenylphosphine) palladium dichloride is 100:0.5:1.7.
7. 7. The preparation method according to claim 5, wherein the halogenated aromatic hydrocarbon monomer and the alkyne-containing monomer in the step (2) are respectively 2, 5-dibromoaniline and tetrakis (4-ethynylphenyl) methane, and the mass ratio of the halogenated aromatic hydrocarbon monomer, the alkyne-containing monomer and the ferroferric oxide balls contained in the mixed solvent C is 30.1:25:100.
8. 8. A ganoderic acid molecularly imprinted microporous organic network material prepared by the method of any one of claims 1-7.
9. 9. The use of the molecularly imprinted microporous organic network material according to claim 8 in enrichment and detection of ganoderic acid substances.
10. 10. The use according to claim 9, wherein the ganoderic acid comprises ganoderic acid a, ganoderic acid B, ganoderic acid a, ganoderic acid B.

Description

Preparation and application of molecular imprinting microporous organic network composite material for selectively enriching ganoderic acid substances Technical Field The invention belongs to the field of material preparation, and in particular relates to synthesis of a molecular imprinting magnetic microporous organic network material and application of the molecular imprinting magnetic microporous organic network material in efficient adsorption and high-sensitivity detection of ganoderic acid substances. Background Ganoderma lucidum is a precious Chinese medicinal material, and is known as "Xian Cao", and has wide medicinal value in works such as Shen nong Ben Cao Jing (Shen nong's herbal), bai Pu Zi (apocynum venetum), xin Xiu Ben Cao (New revised materia Medica). The 2025 edition of Chinese pharmacopoeia clearly records and records that the ganoderma lucidum is fruiting body of Polyporaceae fungi ganoderma lucidum or ganoderma sinensis, has the effects of treating restlessness of heart mind, insomnia and palpitation, cough and asthma due to lung deficiency, consumptive disease and shortness of breath, anorexia, and the like, and confirms the status of homology of medicine and food. With the advancement of modern research of traditional Chinese medicines, systematic research on the chemical components of ganoderma lucidum is attracting attention. Ganoderma contains triterpene, polysaccharide, steroid, protein, nucleoside, vitamins, etc. Ganoderma triterpene compounds have become an important index for evaluating Ganoderma quality, and ganoderic acids are the most representative active ingredients in Ganoderma triterpene, accounting for 70% -95% of total triterpene content, and have become important in research. The modern medicine has reported that ganoderic acid substances have remarkable auxiliary treatment effects in the aspects of resisting tumor, regulating immunity, protecting liver and kidney, resisting inflammation, inhibiting bacteria, reducing blood fat and blood sugar and the like. In view of the above, quantitative analysis of ganoderic acid substances is developed in depth, and the method has important research significance. In an actual sample, the content of ganoderic acid substances is low, and stronger matrix interference exists, so that direct detection of ganoderic acid substances is quite difficult. Therefore, a proper pretreatment method is needed to effectively enrich trace ganoderic acid before analyzing the sample. Magnetic Solid Phase Extraction (MSPE) has become a research hotspot in recent years due to its advantages of easy operation and rapid separation. In the MSPE technology, the selection of the adsorbent is critical, the performance of the adsorbent directly influences the enrichment effect of the target object, and the recovery rate and the selectivity of the pretreatment and the subsequent analysis method are finally determined. Disclosure of Invention In order to solve the technical problems, the invention provides a synthesis method of a molecular imprinting magnetic microporous organic network material, and the obtained material has the characteristics of large specific surface area, strong selective recognition, high adsorption capacity and the like, contains rich delocalized pi bonds, carboxyl groups and amino groups, can generate stronger hydrophobic interaction, hydrogen bonding interaction and pi-pi interaction with ganoderic acid substances containing active sites such as steroid rings, hydroxyl groups and carbonyl groups, can be used as an adsorbent of MSPE, is used for efficiently enriching trace ganoderic acid in complex samples, has simple and quick extraction process, and is expected to be widely applied to the field of sample pretreatment. The Microporous Organic Network (MONs) material is prepared by Sonogashira reaction based on aromatic alkyne and aromatic halide, has the advantages of easy modification of structure, high specific surface area, rich pore structure, simple synthesis and the like, and is gradually popularized in application in sample pretreatment. However, the Mons materials generally suffer from insufficient selectivity. In contrast, molecular Imprinted Polymers (MIPs) can achieve specific adsorption of targets by constructing imprinted cavities that are precisely matched with template molecules on spatial structures and functional groups. And (3) compositing the magnetic microspheres with MONs to obtain the magnetic MONs with high specific surface area, and further constructing a molecular imprinting layer on the surface of the magnetic microspheres to prepare the molecular imprinting magnetic microporous organic network composite material (MMON@OA-MAA) for selectively extracting ganoderic acid substances. The material not only improves the selective recognition capability of ganoderic acid target substances, but also effectively increases the adsorption capacity, and realizes the synergistic enhancement of high selectivity and large