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CN-121490743-B - Magnetic composite material for detecting flavonoid compound, preparation method, detection method and application of preparation standard substance

CN121490743BCN 121490743 BCN121490743 BCN 121490743BCN-121490743-B

Abstract

The invention discloses a magnetic composite material for detecting a flavonoid compound, a preparation method, a detection method and application of a preparation standard substance, and belongs to the technical field of analytical chemistry. The magnetic composite material comprises a magnetic nanoparticle inner core, a first shell layer of a double lanthanide Metal Organic Framework (MOF) and a second shell layer of a Covalent Organic Framework (COF) which are sequentially coated on the surface of the magnetic nanoparticle inner core, and phenylboronic acid groups grafted on the surface of the second shell layer. The material realizes high-efficiency capture and enrichment by utilizing the specific covalent bonding of the phenylboronic acid and the characteristic o-diphenol hydroxyl of the flavonoid compound, promotes energy transfer through the double lanthanide MOF shell layers, provides a high specific surface area and an ordered diffusion channel for the COF shell layers, and facilitates the rapid separation of the magnetic core, thereby jointly realizing high-selectivity identification of the flavonoid compound. The material has the advantages of high sensitivity, strong matrix interference resistance, rapid and simple detection and the like, and is suitable for the accurate analysis of flavone compounds in complex samples and the development of related standard substances.

Inventors

  • LI FUKAI
  • LI LIANG
  • ZHOU JIAN
  • YANG MENGRUI

Assignees

  • 中国农业科学院农业质量标准与检测技术研究所

Dates

Publication Date
20260508
Application Date
20260112

Claims (11)

  1. 1. The magnetic composite material for detecting the flavonoid compound is characterized by comprising an inner core, a first shell layer coated on the surface of the inner core, a second shell layer coated on the surface of the first shell layer, and phenylboronic acid groups grafted on the surface of the second shell layer; the inner core is a magnetic nanoparticle; The first shell layer is a double-lanthanide metal organic framework compound, the double-lanthanide metal organic framework compound comprises two different lanthanide metal ions, and a first organic ligand of the double-lanthanide metal organic framework compound is an aromatic compound containing amino groups and at least two carboxyl groups; The two different lanthanide metal ions are selected from any two of terbium, europium, samarium, dysprosium, cerium and gadolinium; The second shell layer is a covalent organic framework compound, the covalent organic framework compound is formed by connecting a second organic ligand and a third organic ligand through a covalent bond, the second organic ligand is a polyaldehyde compound or a polyhydrazide compound, and the third organic ligand is an aromatic compound containing amino and carboxyl at the same time.
  2. 2. The magnetic composite of claim 1, wherein the first organic ligand is selected from at least one of 2-amino terephthalic acid, 2, 5-diamino terephthalic acid; And/or the second organic ligand is selected from at least one of 1,3, 5-trimethyl phloroglucinol, trimellitic aldehyde and 1, 4-dihydrazinyl benzene, and the third organic ligand is selected from at least one of 2, 5-dianilino terephthalic acid, 2-amino terephthalic acid and 3, 5-diamino benzoic acid; and/or the magnetic nano particles are selected from at least one of ferroferric oxide, cobalt ferrite, nickel ferrite and manganese ferrite.
  3. 3. The magnetic composite of claim 2, wherein the two different lanthanide metal ions are terbium and europium; and/or the first organic ligand is 2-amino terephthalic acid; and/or the second organic ligand is 1,3, 5-trimethyl phloroglucinol, and the third organic ligand is 2, 5-dianilino terephthalic acid; and/or, the magnetic nanoparticle is a ferroferric oxide nanoparticle.
  4. 4. The magnetic composite material according to claim 1, wherein the average particle diameter of the core is 100nm to 500nm; and/or the average thickness of the first shell layer is 10 nm-50 nm, and the average thickness of the second shell layer is 10 nm-100 nm; and/or, the first shell layer and the second shell layer are both provided with porous structures, and the average pore diameter of the porous structures is 5 nm-40 nm.
  5. 5. A method of preparing a magnetic composite material according to any one of claims 1 to 4, comprising the steps of: S102, providing magnetic nano particles, and forming a first shell layer of a lanthanide series bimetallic organic framework compound on the surface of the magnetic nano particles to obtain a first intermediate; S104, forming a second shell layer of a covalent organic framework compound on the surface of the first intermediate to obtain a second intermediate; s106, grafting phenylboronic acid groups on the surface of the second intermediate to obtain the magnetic composite material.
  6. 6. The preparation method of claim 5, wherein step S102 comprises dispersing magnetic nanoparticles, a first lanthanide metal salt, a second lanthanide metal salt and a first organic ligand in a mixed aqueous solution of N, N-dimethylformamide and ethanol, reacting at 100-150 ℃ for 12-72 hours in a high-pressure reaction kettle, naturally cooling to room temperature after the reaction, performing adsorption separation by an external magnet, and washing with deionized water and ethanol to obtain a first intermediate; Wherein the mole ratio of the first lanthanide metal salt to the second lanthanide metal salt to the first organic ligand is (0.5-5): 1, and the dosage ratio of the magnetic nano-particles to the first organic ligand is (0.5-5) g/1 mmol; The volume ratio of N, N-dimethylformamide, ethanol and water in the mixed aqueous solution is (1-3): 1:1, and the consumption of the mixed aqueous solution corresponding to each gram of magnetic nano particles is 100-200 mL.
  7. 7. The preparation method of the compound as claimed in claim 5, wherein the step S104 comprises the steps of dispersing the first intermediate obtained in the step S102 in N, N-dimethylformamide by ultrasonic, adding a second organic ligand, a third organic ligand and an acetic acid solution, uniformly mixing, performing freeze thawing and degassing circulation for 3-5 times, then reacting at 100-150 ℃ for 48-96 h under a sealing condition, cooling to room temperature, collecting the product, cleaning with tetrahydrofuran, then soaking in acetone for 48-96 h, and then drying to obtain a second intermediate; The dosage ratio of the first intermediate to the N, N-dimethylformamide is 1 g (20-50 ml), the mass ratio of the first intermediate to the second organic ligand to the third organic ligand is 1 (1-5), the volume ratio of the N, N-dimethylformamide to the acetic acid solution is 2-5, the concentration of the acetic acid solution is 2-5 mol/L.
  8. 8. The method according to claim 5, wherein step S106 comprises dispersing the second intermediate obtained in step S104 in N, N-dimethylformamide, adding 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide and N-hydroxysuccinimide, stirring for 10 minutes to 30 minutes to activate carboxyl groups, adding 3-aminophenylboronic acid dispersed in N, N-dimethylformamide dropwise after the carboxyl groups are activated, stirring and reacting for 8 hours to 24 hours, washing the separated solid with N, N-dimethylformamide, ethanol and water in sequence, and then drying in vacuum to obtain the magnetic composite material; The dosage ratio of the second intermediate to the dispersed N, N-dimethylformamide is 1 g, 30 ml-60 ml, the mass ratio of the second intermediate to the 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide to the N-hydroxysuccinimide is 1 (0.1-3), and the mass ratio of the second intermediate to the 3-aminophenylboronic acid is 1 (0.1-5).
  9. 9. A method for detecting a flavone compound, comprising dispersing the magnetic composite material according to any one of claims 1 to 4 or the magnetic composite material prepared by the method according to any one of claims 5 to 8 in a solvent to form a composite material dispersion, mixing the composite material dispersion with a solution to be detected containing a flavone compound to form a detection mixture, subjecting the detection mixture to a fluorescent measurement under an ultraviolet lamp, and detecting the flavone compound by using fluorescence response intensity.
  10. 10. A method for detecting a flavone compound, which is characterized by comprising the steps of modifying the magnetic composite material prepared by the preparation method according to any one of claims 1 to 4 or the magnetic composite material prepared by the preparation method according to any one of claims 5 to 8 on the surface of a working electrode to form a modified electrode, placing the modified electrode in a solution to be detected containing the flavone compound for electrochemical measurement, and detecting the flavone compound by measuring a characteristic redox current signal of the flavone compound.
  11. 11. Use of a magnetic composite material according to any one of claims 1 to 4 or a magnetic composite material prepared by a method according to any one of claims 5 to 8 for the preparation of a flavonoid compound standard substance.

Description

Magnetic composite material for detecting flavonoid compound, preparation method, detection method and application of preparation standard substance Technical Field The invention belongs to the technical field of analytical chemistry, and particularly relates to a magnetic composite material for detecting a flavonoid compound, a preparation method, a detection method and application of a preparation standard substance. Background Flavonoid compounds are widely used in alcoholic beverages such as fruits, vegetables, tea, wine and the like. Because of their antioxidant, antiallergic, anticancer, antiviral and anti-inflammatory properties, they have a benign impact on the health of the nervous system, respiratory system, cardiovascular and skin tissue injuries, and are therefore of great interest. Based on these characteristics, a simple, accurate and reliable detection method for flavone compounds is of great importance. Traditional detection methods of flavone compounds include high performance liquid chromatography, surface enhanced raman spectroscopy, capillary electrophoresis, and the like. Although each of these methods has advantages, there are significant limitations in that expensive laboratory instruments, complex pretreatment steps, specialized operators, and lengthy read times are required, and potential limitations in sensitivity, selectivity, cost, and interference problems with complex matrix components of real samples may also be faced. Therefore, there is an urgent need to develop efficient, accurate, sensitive and convenient detection methods. It should be noted that this section of the disclosure only provides a background related to the present disclosure, and does not necessarily constitute prior art or known technology. Disclosure of Invention The invention provides a magnetic composite material for detecting a flavone compound, a preparation method, a detection method and application of a preparation standard substance, and at least solves the technical problems that a flavone compound detection method in the prior art depends on a large instrument, is complex in pretreatment and weak in matrix interference resistance. In order to achieve the above object, in a first aspect, the present invention provides a magnetic composite material for detecting a flavone compound, which comprises a core, a first shell layer coated on the surface of the core, a second shell layer coated on the surface of the first shell layer, and phenylboronic acid groups grafted on the surface of the second shell layer, wherein the core is a magnetic nanoparticle, the first shell layer is a bis-lanthanide metal organic framework compound, the bis-lanthanide metal organic framework compound comprises two different lanthanide metal ions, the first organic ligand of the bis-lanthanide metal organic framework compound is an aromatic compound containing at least two carboxyl groups, the second shell layer is a covalent organic framework compound, the covalent organic framework compound is formed by connecting a second organic ligand and a third organic ligand through covalent bonds, the second organic ligand is a polyaldehyde compound or a polyhydrazide compound, and the third organic ligand is an aromatic compound containing both amino groups and carboxyl groups. Preferably, the two different lanthanide metal ions are selected from any two of terbium, europium, samarium, dysprosium, cerium, gadolinium; and/or the first organic ligand is selected from at least one of 2-amino terephthalic acid, 2, 5-diamino terephthalic acid; And/or the second organic ligand is selected from at least one of 1,3, 5-trimethyl phloroglucinol, trimellitic aldehyde and 1, 4-dihydrazinobenzene, and the third organic ligand is selected from at least one of 2, 5-dianiline terephthalic acid, 2-amino terephthalic acid and 3, 5-diaminobenzoic acid; and/or the magnetic nano particles are selected from at least one of ferroferric oxide, cobalt ferrite, nickel ferrite and manganese ferrite. Preferably, the two different lanthanide metal ions are terbium and europium; and/or the first organic ligand is 2-amino terephthalic acid; and/or the second organic ligand is 1,3, 5-trimethyl phloroglucinol and the third organic ligand is 2, 5-diphenylamino terephthalic acid; and/or the magnetic nanoparticles are ferroferric oxide nanoparticles. Preferably, the average particle size of the inner core is 100 nm-500 nm; And/or the average thickness of the first shell layer is 10 nm-50 nm, and the average thickness of the second shell layer is 10 nm-100 nm; and/or the first shell layer and the second shell layer are both porous structures, and the average pore diameter of the porous structures is 5 nm-40 nm. In a second aspect, the present invention provides a method of preparing the magnetic composite of the first aspect, comprising the steps of: S102, providing magnetic nano particles, and forming a first shell layer of a lanthanide series bimetallic organic framewo