CN108452784B - Catecholamine solid phase extraction functional composite material, preparation method and application thereof - Google Patents
Catecholamine solid phase extraction functional composite material, preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a catecholamine solid phase extraction functional composite material, which takes magnetic 3D graphene nanoparticles as a core, and the surface of the composite material is provided with a functional polymer which is mainly synthesized by tetraethoxysilane, mercaptopropyl trimethoxy silane and 2-phenyl acrylic acid, has special affinity sites for catecholamine substances and has a cross-linked network structure. Accordingly, a corresponding preparation method is also established. The solid-phase extraction functional composite material product is used for adsorption and dynamic extraction separation of illegally added trace amount of catecholamine substances such as epinephrine and the like in the analysis pretreatment of cosmetic samples with complex matrixes, can realize rapid separation and detection of the catecholamine substances, has the characteristics of simple preparation method, low cost, high recovery rate of the method, small relative standard deviation, less use of organic solvents, more convenient and rapid solid-phase extraction operation, high efficiency and the like.
Description
Technical Field
The invention belongs to the technical field of cosmetic safety detection, and particularly relates to a catecholamine solid-phase extraction functional composite material, and a preparation method and application thereof.
Background
Catecholamine is a nerve substance containing catechol and amino, epinephrine, norepinephrine and isoproterenol belong to catecholamine substances forbidden by cosmetics, and one or more substances are added into the cosmetics, so that the effects of preventing skin aging, removing wrinkles, increasing skin elasticity and the like are achieved to a certain extent, but excessive use can affect blood circulation of main organs such as a central nervous system, heart and kidney and the like, and ischemia symptoms and functional damage of each system occur. Therefore, the european union 2008 enforces new cosmetic hygiene standards, which stipulate such drugs as banned substances. In the 'cosmetic hygiene code' (2007 edition), which was issued by Ministry of health in China, 1286 common forbidden substances in the list of substances for restricting cosmetics are revised, and the 3 compounds are included. However, driven by commercial interest in recent years, the phenomenon of the abuse of catecholamine substances in the cosmetic industry tends to be increased, and the drugs which are used seriously are taken as specific components for removing wrinkles and increasing skin elasticity by bad manufacturers and beauty parlors, and words of exaggerated efficacy such as 'rapid wrinkle removal' and 'easy anti-aging' are often shown in the propaganda advertisement. However, consumers do not know the "secret" before and during use, leading to a disruption of the hormonal balance in the body and the development of various diseases. Therefore, catecholamines are added into the cosmetics, which seriously endangers human health.
The cosmetic samples are mostly mixtures composed of various substances, and the residues of the detected harmful substances are often trace or even trace, so that the pretreatment process of the samples is very important for the accuracy and reliability of the analysis result. Solid Phase Extraction (SPE) is an important sample pretreatment method based on chromatographic separation, which has been rapidly developed in recent years. The essence of the solid phase extraction technology is that a solid adsorbent is utilized to adsorb a target substance from a liquid sample and separate the target substance from a matrix and an interfering substance of the sample, and then an eluent is used for elution, so that the aim of separating and enriching the target substance is fulfilled, the detection capability of the target substance, particularly a trace target substance, is enhanced, and the recovery rate of the target substance is further improved.
The 3D graphene is a three-dimensional nanomaterial with the thickness of only one carbon atom, and the structure combines the inherent special properties of the graphene with a three-dimensional porous structure, so that the 3D graphene has the properties of larger specific surface area, more active sites, higher mechanical strength, faster electron and mass transfer and the like, and is widely applied to the aspects of catalysts, sensors, supercapacitors, hydrogen storage, adsorption materials and the like. The 3D graphene is combined with a magnetic separation technology to prepare a novel functional composite material, and the novel functional composite material is applied to sample pretreatment, and has the great advantages of increasing adsorption capacity, improving trace component detection sensitivity, enhancing material durability and the like.
Click chemistry (Click chemistry), an organic synthetic concept first proposed in 2001 by the united states chemist sharp, the nobel prize of chemistry, is another rapid synthetic technique that has brought significant innovation to traditional organic chemistry following combinatorial chemistry. The key point of click chemistry is to form a carbon-heteroatom bond through the splicing of small units under mild reaction conditions, and synthesize various molecules quickly, simply and selectively. Click chemistry reactions have many advantages: if the reaction raw materials are easily available; the reaction condition is mild and simple, is not sensitive to oxygen and water, and does not need to carry out water removal and oxygen removal operations; the reaction operation is simple and the reaction speed is high; the reaction product has good selectivity, few byproducts, no toxic byproducts, high yield and environmental friendliness; the reaction product is single, the product post-treatment is simple, and the separation and purification are easy. The sulfydryl-alkene click chemistry reaction is novel click chemistry which does not need metal as a catalyst, under the condition of heating or ultraviolet illumination and under the action of an initiator, alkenyl can be subjected to free radical polymerization with sulfydryl in a functional monomer, the selectivity of the functional monomer is expanded, and functional groups on the surface of a composite material are more flexible and diversified. At present, thiol-ene click chemistry has penetrated into many research fields such as life, medicine, surface modification, polymer, functional materials, etc.
Disclosure of Invention
The invention aims to solve the technical problem of providing a catecholamine solid phase extraction functional composite material which is simple in preparation method, low in cost and excellent in performance, and a preparation method and application thereof.
In order to solve the technical problems, the invention adopts the following technical scheme:
a catecholamine solid phase extraction functional composite material takes magnetic 3D graphene nanoparticles as a core, and the surface of the composite material is provided with a functional polymer which is mainly synthesized by tetraethoxysilane, mercaptopropyl trimethoxysilane and 2-phenyl acrylic acid, has special affinity sites for catecholamine substances and has a cross-linked network structure.
The catecholamine solid-phase extraction functional composite material takes 3D graphene as a synergist for Fe3O4Modifying magnetic nanoparticles by taking tetraethoxysilane as a cross-linking agent, mercaptopropyltrimethoxysilane as a mercapto reagent, 2-phenylacrylic acid as a functional molecule and azodiisobutyronitrile as an initiator to Fe3O4The surface of the magnetic nano particle is modified layer by layer to prepare the magnetic nano particle.
Modified Fe3O4The feeding ratio of the magnetic nanoparticles, the ethyl orthosilicate, the mercaptopropyl trimethoxy silane, the 2-phenyl acrylic acid and the azobisisobutyronitrile is 300-900 mg: 2-6 mmol: 3-9 mmol: 0.0375-0.1125 g.
The preparation method of the catecholamine solid-phase extraction functional composite material adopts a mercapto-alkene click chemical surface polymerization method and Fe modified by 3D graphene3O4Taking magnetic nanoparticles as a core, then taking tetraethoxysilane as a cross-linking agent, mercaptopropyltrimethoxysilane as a mercapto reagent, 2-phenyl acrylic acid as a functional molecule and azobisisobutyronitrile as an initiator to perform polymerization reaction, and then washing to remove impurities to obtain the nano-magnetic material.
The preparation method of the catecholamine solid-phase extraction functional composite material comprises the following steps:
(1)3D graphene modified Fe3O4Magnetic nanoparticles
Placing 100-300 mg of 3D graphene into a three-necked flask, adding 50-150 mL of distilled water, carrying out ice-water bath ultrasound for 10min, uniformly mixing, stirring at 300rpm, and taking 1000-3000 mg of Fe3O4Magnetic nanoparticles and 50-150 mL of distilled water are ultrasonically treated for 3min, the mixture is dropwise added into a three-neck flask, and N is filled into the three-neck flask2Reacting for 1h at room temperature for 10min, separating the product from the solution by using a strong magnet, washing the solution for 3 times by using absolute ethyl alcohol, and adding 15mL of absolute ethyl alcohol to disperse the absolute ethyl alcohol to obtain black 3D graphene magnetofluid;
(2) preparation of sulfhydrylation 3D graphene magnetic nanoparticles
Placing 300-900 mg of 3D graphene magnetic nanoparticles into a three-neck flask, adding 50-150 mL of absolute ethyl alcohol and 2-6 mmol of ethyl orthosilicate, ultrasonically dispersing for 3min in ice-water bath, stirring at 360rpm, and filling N2Adding 2-6 mL of acetic acid; taking 2-6 mmol of mercaptopropyl trimethoxy silane and 50-150 mL of absolute ethyl alcohol, carrying out ultrasonic mixing in an ice water bath for 15min, dropwise adding the mixture into a three-necked flask, reacting for 12h at 55 ℃, separating a product from a solution by using a strong magnet, washing for 3 times by using the absolute ethyl alcohol, and adding 5mL of absolute ethyl alcohol for dispersion to obtain a sulfhydrylation 3D graphene magnetofluid;
(3) preparation of catecholamine solid phase extraction functional composite material by adopting sulfydryl-alkene click chemical surface polymerization method
Placing 300-900 mg of sulfhydrylation 3D graphene magnetic nanoparticles into a three-neck flask, adding 50-150 mL of absolute ethyl alcohol, performing ultrasonic dispersion for 3min, stirring at 360rpm, and filling N2Taking 3-9 mmol of 2-phenyl acrylic acid, 0.0375-0.1125 g of azobisisobutyronitrile and 50-150 mL of absolute ethyl alcohol, dispersing by ultrasound for 10min, dropwise adding into a three-necked flask, reacting for 2h at 65 ℃, reacting for 2h at 75 ℃, separating the product from the solution by using a strong magnet, washing for 3 times by using the absolute ethyl alcohol, putting the obtained product into a filter paper cylinder, soxhlet extracting for 2-6 h by using 100-300 mL of absolute ethyl alcohol as an eluent, removing impurities, and naturally air-drying to obtain the catecholamine solid-phase extraction functional composite material.
Fe3O4The magnetic nano particles are prepared by adopting a chemical coprecipitation method according to the following steps: 10.6g of FeCl3·6H2O，4.0g FeCl2·4H2Placing O in a three-neck flask containing 200mL of deionized water, dissolving with ultrasound, starting stirring, introducing N2Deoxidizing, heating to 80 ℃, adding 25mL of strong ammonia water, reacting for 6h, separating the product from the solution by strong magnet, and washing Fe by deionized water3O4Adding 15mL of water to disperse until the solution is neutral to obtain black Fe3O4A magnetic fluid;
the 3D graphene is prepared by the following steps: taking 10mL of graphene oxide with 2mg/mL of graphene oxide, performing ultrasonic dispersion uniformly, sealing in a high-temperature reaction kettle with a 20mL polytetrafluoroethylene lining, reacting at 180 ℃ for 12h, cooling to room temperature, taking out the 3D graphene, sucking surface moisture with filter paper, and storing;
the catecholamine solid phase extraction functional composite material is applied to separation, enrichment and purification of catecholamine substance residues in samples.
The catecholamine solid phase extraction functional composite material is applied to the analysis pretreatment of cosmetic samples containing catecholamine substances.
The application is carried out according to the following steps:
(1) activation of
Taking catecholamine solid phase extraction functional composite material 25mg, placing in a conical flask with a plug, activating with 3mL of methanol, discarding waste liquid, rinsing with 3mL of acetonitrile, removing methanol on the surface of the functional composite material, and discarding the waste liquid; then 3mL of acetonitrile is used for balancing, and waste liquid is discarded; obtaining the activated functional composite material;
(2) extraction of
Precisely weighing 0.5g of a cosmetic sample, placing the cosmetic sample in a centrifuge tube with a plug, accurately transferring 2mL of saturated sodium chloride solution and 10mL of acetonitrile, ultrasonically extracting for 10min in an ice water bath, centrifuging for 10min at 10000rpm at 4 ℃, accurately transferring 5mL of acetonitrile extract at the upper layer, adding the acetonitrile extract into the conical bottle with a plug in the step (1), and mixing the acetonitrile extract with the activated functional composite material; extracting under oscillation for 80min, separating with magnetic field, and discarding waste liquid;
(3) leaching with water
Leaching the functional composite material treated in the step (2) by using 3mL of acetonitrile, and discarding waste liquid;
(4) elution is carried out
Eluting the functional composite material by using 2-6 mL of 0.1% formic acid aqueous solution-methanol with the volume ratio of 98:2 as an eluent, and collecting the eluent; blowing at 35 deg.C with nitrogen to obtain residue, dissolving the residue with 1mL eluent, filtering with 0.45 μm filter head, and analyzing by HPLC.
Aiming at the problems of abuse and difficult detection of the existing catecholamine substances, the inventor designs and prepares a catecholamine solid phase extraction functional composite material, which takes magnetic 3D graphene nanoparticles as cores, and the surface of the composite material is provided with a functional polymer which is mainly synthesized by tetraethoxysilane, mercaptopropyltrimethoxysilane and 2-phenyl acrylic acid, has special affinity sites for the catecholamine substances and has a cross-linked network structure. Accordingly, a corresponding preparation method is also established, namely Fe modified by 3D graphene3O4The magnetic nano particles (magnetic material) are taken as a core, and then tetraethoxysilane, mercaptopropyl trimethoxy silane and 2-phenyl acrylic acid are respectively bonded on the surface of the magnetic core layer by layer through silanization reaction and mercapto-alkene click chemical surface polymerization reaction to form a non-magnetic polymer. The solid phase extraction functional composite material obtained by the invention has the characteristic of dynamic separation of magnetic materials, and can be conveniently and quickly separated from a sample matrix under the action of an external magnetic field after the extraction of target substance catecholamine substances is finished, so that the solid phase extraction functional composite material is particularly suitable for the separation and enrichment of target substances in a complex system.
Experimental research shows that compared with the prior art, the invention has the following outstanding advantages:
1. the preparation method of the catecholamine solid phase extraction functional composite material based on the sulfydryl-alkene click chemistry and the 3D graphene synergism is simple to operate and wide in applicability.
2. Before polymerization, 3D graphene is used for Fe3O4The surface of the magnetic nano particle is modified, so that the fat solubility of the magnetic nano particle is enhanced, the problem of compatibility of metal oxide and organic polymer is solved, and the magnetic nano particle becomes a magnetic core of a functional polymer. Since the graphene with the three-dimensional structure has the 3D porous structure, the graphene with the three-dimensional structure not only has the specific object of the graphenePhysical and chemical properties, more excellent electrochemical properties, larger specific surface area and stronger mechanical properties than those of a two-dimensional planar graphene material, and has great advantages of increasing adsorption capacity, improving trace component detection sensitivity, enhancing material durability and the like.
3. The 3D graphene is subjected to surface modification by utilizing sulfydryl-alkene click chemistry, functional molecules capable of forming hydrogen bond action, ion association action and pi-pi interaction with catecholamine substances are connected to the surface of the magnetic 3D graphene, a polymer with a special affinity site and a cross-linked network structure is formed, and the specific adsorption performance of the functional composite extraction material is favorably improved.
4. The obtained solid phase extraction functional composite material has the magnetic core, so that in the process of adsorbing and extracting the target substance, a filling column is not required to be filled, and the solid phase extraction functional composite material is directly added into the extracting solution of a sample to be detected for adsorption and enrichment, so that the target substance can be quickly extracted; after extraction is finished, high-speed centrifugation is not needed, the functional composite material can be gathered only by using an external magnetic field, separation from a sample matrix is realized, matrix and impurity interference in the sample are quickly eliminated, analysis steps are greatly simplified, analysis time is saved, consumption of an organic solvent is reduced, and rapid separation and detection of a target substance are realized.
Detailed Description
Example 1
Preparation of catecholamine solid phase extraction functional composite material
(1) Preparation of Fe by chemical coprecipitation method3O4Magnetic nanoparticles
10.6g of FeCl3·6H2O，4.0g FeCl2·4H20 is put into a three-neck flask filled with 200mL deionized water, dissolved by ultrasonic, stirred and introduced with N2Deoxidizing, heating to 80 ℃, adding 25mL of strong ammonia water, reacting for 6h, separating the product from the solution by strong magnet, and washing Fe by deionized water304Adding 15mL of water to disperse until the solution is neutral to obtain black Fe304Magnetic fluid (i.e. Fe)3O4Magnetic nanoparticles);
(2) preparation of 3D graphene
Taking 10mL of graphene oxide with 2mg/mL of graphene oxide, performing ultrasonic dispersion uniformly, sealing in a high-temperature reaction kettle with a 20mL polytetrafluoroethylene lining, reacting at 180 ℃ for 12h, cooling to room temperature, taking out the 3D graphene, sucking surface moisture with filter paper, and storing;
(3)3D graphene modified Fe304Magnetic nanoparticles
Placing 100mg of 3D graphene in a three-neck flask, adding 50mL of distilled water, performing ultrasonic treatment in ice water bath for 10min, mixing uniformly, stirring at 300rpm, and taking 1000mg of Fe3O4Magnetic nanoparticles and 50mL of distilled water are ultrasonically treated for 3min, the mixture is dropwise added into a three-neck flask, and N is filled into the three-neck flask2Reacting for 1h at room temperature for 10min, separating the product from the solution with strong magnet, washing with anhydrous ethanol for 3 times, adding 15mL of anhydrous ethanol, and dispersing to obtain black 3D graphene magnetofluid (Fe)3O4@3DG)；
(4) Preparation of sulfhydrylation 3D graphene magnetic nanoparticles
Placing 300mg of 3D graphene magnetic nanoparticles into a three-neck flask, adding 50mL of absolute ethyl alcohol and 2mmol of ethyl orthosilicate, ultrasonically dispersing for 3min in ice-water bath, stirring at 360rpm, and filling N22mL of acetic acid was added. Taking 2mmol of mercaptopropyl trimethoxy silane and 50mL of absolute ethyl alcohol, carrying out ultrasonic treatment in ice water bath for 15min, uniformly mixing, dropwise adding the mixture into a three-necked flask, reacting for 12h at 55 ℃, separating a product from a solution by using a strong magnet, washing 3 times by using the absolute ethyl alcohol, adding 5mL of absolute ethyl alcohol, and dispersing to obtain the sulfhydrylation 3D graphene magnetofluid (Fe)3O4@3DG@SiO2-SH)；
(5) Preparation of catecholamine solid phase extraction functional composite material by adopting sulfydryl-alkene click chemical surface polymerization method
Placing 300mg of sulfhydrylation 3D graphene magnetic nanoparticles into a three-neck flask, adding 50mL of absolute ethyl alcohol, performing ultrasonic dispersion for 3min, stirring at 360rpm, and filling N2Taking 3mmol of 2-phenyl acrylic acid, 0.0375g of azobisisobutyronitrile and 50mL of absolute ethyl alcohol, performing ultrasonic dispersion for 10min, dropwise adding the mixture into a three-necked flask, reacting at 65 ℃ for 2h and at 75 ℃ for 2h, separating a product from a solution by using a strong magnet, washing the product with the absolute ethyl alcohol for 3 times, putting the obtained product into a filter paper cylinder, and adding 100mL of absolute ethyl alcoholSoxhlet extraction with alcohol as eluent for 2 hr, removing impurities, and air drying to obtain catecholamine solid phase extraction functional composite material (Fe)3O4@3DG@SiO2-SH@Ph-COOH)。
Respectively adopting a Vibration Sample Magnetometer (VSM), a Fourier infrared spectrum (FT-IR), a Scanning Electron Microscope (SEM), energy spectrum analysis (EDS), particle size Distribution (DLS), thermogravimetric analysis (TGA) and other instrument analysis means to analyze Fe3O4、Fe3O4@3DG、Fe3O4@3DG@SiO2-SH、Fe3O4@3DG@SiO2The magnetization performance, structure, morphology, thermal stability and the like of the four magnetic nanoparticles such as-SH @ Ph-COOH are characterized. The results show that Fe is present in the magnetic core3O4The 3D graphene modification, the sulfydryl silanization modification and the click synthesis of the 2-phenyl acrylic acid which are carried out layer by layer on the surface are successful, and the fact that the synthesized functional polymer has a core-shell structure is shown.
Secondly, the catecholamine solid phase extraction functional composite material is applied to the separation, enrichment and purification of catecholamine substances in moisturizing water
(1) Taking 25mg of the catecholamine solid phase extraction functional composite material obtained in the embodiment, placing the catecholamine solid phase extraction functional composite material in a conical flask with a stopper, activating with 3mL of methanol, discarding waste liquid, rinsing with 3mL of acetonitrile, removing the methanol on the surface of the functional composite material, and discarding the waste liquid; then 3mL of acetonitrile is used for balancing, and waste liquid is discarded; obtaining the activated functional composite material;
(2) accurately weighing a proper amount of commercially available cosmetics (moisturizing water), accurately adding a proper amount of catecholamine mixed standard solution, and preparing four samples (1 microgram/g, 5 microgram/g, 10 microgram/g and 20 microgram/g) with different standard adding levels. Accurately weighing 0.5g of a standard sample, placing the standard sample in a centrifuge tube with a plug, accurately transferring 2mL of saturated sodium chloride solution and 10mL of acetonitrile, ultrasonically extracting for 10min in an ice-water bath, centrifuging for 10min at 10000rpm at 4 ℃, accurately transferring 5mL of acetonitrile extract at the upper layer, adding the acetonitrile extract into the conical flask with the plug in the step (1), and mixing with the activated functional composite material; extracting for 80min under the action of oscillation, separating by magnetic field after extraction is finished, and discarding sample waste liquid; leaching the functional composite material by using 3mL of acetonitrile, and removing waste liquid;
(3) the volume ratio of 98:2, eluting with 0.1% formic acid water solution-methanol (2mL × 3 times), and collecting the eluate; blowing at 35 deg.C with nitrogen to obtain residue, dissolving the residue with 1mL eluent, filtering with 0.45 μm filter head, and analyzing by HPLC.
As a result: the catecholamine solid-phase extraction functional composite material obtained in the example 1 has the capability of separating, enriching and purifying catecholamine substances in moisturizing water, and has the standard recovery rates of 92.11-98.09%, 94.19-100.2% and 94.66-105.4% for adrenaline, noradrenaline and isoproterenol in the moisturizing water respectively, and the relative standard deviations of 0.24-0.87%, 0.28-0.82% and 0.64-1.30% respectively.
Example 2
Preparation of catecholamine solid phase extraction functional composite material
Steps (1) and (2) were the same as in example 1.
(3)3D graphene modified Fe3O4Magnetic nanoparticles
Putting 200mg of 3D graphene into a three-neck flask, adding 100mL of distilled water, carrying out ultrasonic treatment in an ice-water bath for 10min, uniformly mixing, stirring at 300rpm, and taking 2000mg of Fe3O4Magnetic nanoparticles and 100mL of distilled water are ultrasonically treated for 3min, the mixture is dropwise added into a three-neck flask, and N is filled into the three-neck flask2And (3) reacting at room temperature for 1h for 10min, separating the product from the solution by using a strong magnet, washing the solution for 3 times by using absolute ethyl alcohol, and adding 15mL of absolute ethyl alcohol to disperse the absolute ethyl alcohol to obtain black 3D graphene magnetofluid.
(4) Preparation of sulfhydrylation 3D graphene magnetic nanoparticles
Placing 600mg of 3D graphene magnetic nanoparticles into a three-neck flask, adding 100mL of absolute ethyl alcohol and 4mmol of ethyl orthosilicate, ultrasonically dispersing for 3min in ice-water bath, stirring at 360rpm, and filling N24mL of acetic acid was added. Taking 4mmol of mercaptopropyl trimethoxy silane and 100mL of absolute ethyl alcohol, carrying out ultrasonic treatment in an ice water bath for 15min, uniformly mixing, dropwise adding the mixture into a three-necked flask, reacting for 12h at 55 ℃, separating a product from a solution by using a strong magnet, washing for 3 times by using the absolute ethyl alcohol, and adding 5mL of the absolute ethyl alcohol for dispersion to obtain the sulfhydrylation 3D graphene magnetofluid;
(5) preparation of catecholamine solid phase extraction functional composite material by adopting sulfydryl-alkene click chemical surface polymerization method
Placing 600mg of sulfhydrylation 3D graphene magnetic nanoparticles into a three-neck flask, adding 100mL of absolute ethyl alcohol, performing ultrasonic dispersion for 3min, stirring at 360rpm, and filling N2Taking 6mmol of 2-phenyl acrylic acid, 0.075g of azobisisobutyronitrile and 100mL of absolute ethyl alcohol, dispersing by ultrasound for 10min, dropwise adding into a three-necked flask, reacting at 65 ℃ for 2h and at 75 ℃ for 2h, separating a product from a solution by using a strong magnet, washing with the absolute ethyl alcohol for 3 times, putting the obtained product into a filter paper cylinder, soxhlet extracting for 4h by using 200mL of absolute ethyl alcohol as an eluent, removing impurities, and naturally air-drying to obtain the functional composite material.
The structural characterization of the functional composite was the same as in example 1.
Secondly, the catecholamine solid phase extraction functional composite material is applied to the separation, enrichment and purification of catecholamine substances in the moisturizing cream, and the specific operation refers to the treatment of the catecholamine solid phase extraction functional composite material on moisturizing water in example 1.
As a result: the catecholamine solid-phase extraction functional composite material obtained in the example 2 has the capability of separating, enriching and purifying catecholamine substances in the moisturizing cream, and the standard recovery rates of adrenaline, noradrenaline and isoproterenol in a moisturizing cream sample are respectively 94.90-98.98%, 94.41-105.4% and 97.04-107.8%, and the relative standard deviations are respectively 0.21-1.09%, 0.11-0.74% and 0.36-1.34%.
Example 3
Preparation of catecholamine solid phase extraction functional composite material
Steps (1) and (2) were the same as in example 1.
(3)3D graphene modified Fe3O4Magnetic nanoparticles
Placing 300mg of 3D graphene in a three-neck flask, adding 150mL of distilled water, carrying out ice-water bath ultrasound for 10min, uniformly mixing, stirring at 300rpm, and taking 3000mg of Fe3O4Magnetic nanoparticles, 150mL of distilled water, ultrasonic treatment for 3min, dropwise adding into a three-neck flask, and charging N2Reacting for 10min at room temperature for 1h, separating the product from the solution with strong magnet, washing with anhydrous ethanol for 3 times, adding 15mL of anhydrous ethanol, and dispersing to obtainBlack 3D graphene magnetic fluid.
(4) Preparation of sulfhydrylation 3D graphene magnetic nanoparticles
Placing 900mg of 3D graphene magnetic nanoparticles into a three-neck flask, adding 150mL of absolute ethyl alcohol and 6mmol of ethyl orthosilicate, ultrasonically dispersing for 3min in ice-water bath, stirring at 360rpm, and filling N26mL of acetic acid was added. Taking 6mmol of mercaptopropyl trimethoxy silane and 150mL of absolute ethyl alcohol, carrying out ultrasonic treatment in an ice water bath for 15min, uniformly mixing, dropwise adding the mixture into a three-necked flask, reacting for 12h at 55 ℃, separating a product from a solution by using a strong magnet, washing 3 times by using the absolute ethyl alcohol, and adding 5mL of the absolute ethyl alcohol for dispersion to obtain the sulfhydrylation 3D graphene magnetofluid;
(5) preparation of catecholamine solid phase extraction functional composite material by adopting sulfydryl-alkene click chemical surface polymerization method
Placing 900mg of sulfhydrylation 3D graphene magnetic nanoparticles into a three-neck flask, adding 150mL of absolute ethyl alcohol, performing ultrasonic dispersion for 3min, stirring at 360rpm, and filling N2Taking 9mmol of 2-phenylacrylic acid, 0.1125g of azobisisobutyronitrile and 150mL of absolute ethyl alcohol, performing ultrasonic dispersion for 10min, dropwise adding the mixture into a three-necked flask, reacting at 65 ℃ for 2h and at 75 ℃ for 2h, separating a product from a solution by using a strong magnet, washing the product with the absolute ethyl alcohol for 3 times, putting the obtained product into a filter paper cylinder, performing Soxhlet extraction for 6h by using 300mL of absolute ethyl alcohol as an eluent, removing impurities, and naturally drying in the air to obtain the functional composite material.
The structural characterization of the functional composite was the same as in example 1.
Secondly, the catecholamine solid phase extraction functional composite material is applied to the separation, enrichment and purification of catecholamine substances in the light sensation face cream
The specific operation refers to the treatment of the catecholamine solid phase extraction functional composite material on the moisturizing water in the example 1.
As a result: the catecholamine solid-phase extraction functional composite material obtained in the example 3 has the capability of separating, enriching and purifying catecholamine substances in a photosensitive cream, and the labeling recovery rates of adrenaline, noradrenaline and isoproterenol in a photosensitive cream sample are respectively 94.70-98.05%, 93.40-103.6% and 92.74-109.6%, and the relative standard deviations are respectively 0.12-1.10%, 0.35-1.13% and 0.38-0.78%.
Example 43 study of Effect of graphene on adsorption Capacity of functional composite
Preparation of functional composite material
The preparation of the 3D graphene synergistic functional composite material comprises the following three processes: 3D graphene vs Fe3O4Modifying the surface to form 3D graphene magnetic nanoparticles (Fe)3O4@3 DG); in Fe3O4The surface of @3DG is modified by mercapto silanization to form Fe3O4@3DG@SiO2-SH; linking an enoate functional molecule to Fe using thiol-ene click chemistry3O4@3DG@SiO2-SH surface, forming a functional polymer (Fe) with specific affinity sites for catecholamines and a cross-linked network structure3O4@3DG@SiO2-SH@Ph-COOH)。
In order to evaluate the synergistic effect of the 3D graphene on the adsorption capacity of the functional composite material, two functional composite materials are synthesized. Namely to Fe3O4Surface modification, Material 1 (Fe) under the same experimental conditions3O4@3DG@SiO2-SH @ Ph-COOH) was modified with 3D graphene, material 2 (Fe)3O4@SiO2-SH @ Ph-COOH) is directly subjected to a mercaptosilylation modification without using 3D graphene.
Second, adsorption experiment of functional composite material to adrenalin
Accurately weighing 25mg of the composite material 1 and the composite material 2, respectively placing the composite material 1 and the composite material 2 in conical flasks with stoppers, activating the conical flasks with methanol for 2 times, balancing the conical flasks with acetonitrile for 2 times, adding 10mL of 1mg/mL epinephrine solution, placing the two conical flasks in an oscillator, oscillating the conical flasks at room temperature for 80min, and separating a supernatant from the composite material under the action of an external magnetic field. And precisely transferring a proper amount of supernatant, fixing the volume with acetonitrile, measuring the absorbance at 280nm, and calculating the adsorption capacity.
According to the formula Q ═ C0-Ce) V/W, calculating the adsorption amount of the composite material through the concentration change of the solution before and after adsorption. Wherein Q is equilibrium adsorption capacity (mg/g); c0And Ce is epinephrine solution respectivelyInitial concentration to equilibrium concentration of adsorption (mg/mL); v is the volume of solution (mL); w is the mass (g) of the functional composite material.
Research result of synergistic effect of 3D graphene on adsorption capacity of functional composite material
The adsorption experiment was performed on the above-described epinephrine solution using the material 1 and the material 2, respectively, and the results are shown in table 1.
Table 13D effect of graphene on adsorption properties of functional composites
3D graphene vs Fe3O4The surface is modified, so that the adsorption capacity of the functional composite material is remarkably improved, and the 3D graphene has an obvious synergistic function. The 3D graphene is a material with a three-dimensional porous structure formed by stacking two-dimensional graphene layers, so that the specific surface area of the material is greatly increased, and the adsorption capacity of a functional polymer is obviously increased.
Claims (8)
1. A catecholamine solid phase extraction functional composite material is characterized in that magnetic 3D graphene nanoparticles are used as a core, and a functional polymer which is mainly synthesized by tetraethoxysilane, mercaptopropyl trimethoxy silane and 2-phenyl acrylic acid, has special affinity sites for catecholamine substances and has a cross-linked network structure is arranged on the surface of the composite material; the composite material is prepared by the following method: fe modified by 3D graphene by adopting a sulfydryl-alkene click chemical surface polymerization method3O4Taking magnetic nanoparticles as a core, then taking tetraethoxysilane as a cross-linking agent, mercaptopropyltrimethoxysilane as a mercapto reagent, 2-phenyl acrylic acid as a functional molecule and azobisisobutyronitrile as an initiator to perform polymerization reaction, and then washing to remove impurities to obtain the nano-magnetic material.
2. The catecholamine solid phase extraction functional composite of claim 1, wherein: the 3D graphene-modified Fe3O4Magnetic nanoparticles and orthosilicic acidThe feeding ratio of the ethyl ester, the mercaptopropyl trimethoxy silane, the 2-phenyl acrylic acid and the azobisisobutyronitrile is 300-900 mg, 2-6 mmol, 3-9 mmol, 0.0375-0.1125 g.
3. A preparation method of a catecholamine solid phase extraction functional composite material is characterized by comprising the following steps:
(1)3D graphene modified Fe3O4Magnetic nanoparticles
Placing 100-300 mg of 3D graphene into a three-necked flask, adding 50-150 mL of distilled water, carrying out ice-water bath ultrasound for 10min, uniformly mixing, stirring at 300rpm, and taking 1000-3000 mg of Fe3O4Magnetic nanoparticles and 50-150 mL of distilled water are ultrasonically treated for 3min, the mixture is dropwise added into a three-neck flask, and N is filled into the three-neck flask2Reacting for 1h at room temperature for 10min, separating the product from the solution by using a strong magnet, washing the solution for 3 times by using absolute ethyl alcohol, and adding 15mL of absolute ethyl alcohol to disperse the absolute ethyl alcohol to obtain black 3D graphene magnetic nanoparticles;
(2) preparation of sulfhydrylation 3D graphene magnetic nanoparticles
Placing 300-900 mg of 3D graphene magnetic nanoparticles into a three-neck flask, adding 50-150 mL of absolute ethyl alcohol and 2-6 mmol of ethyl orthosilicate, ultrasonically dispersing for 3min in ice-water bath, stirring at 360rpm, and filling N2Adding 2-6 mL of acetic acid; taking 2-6 mmol of mercaptopropyl trimethoxy silane and 50-150 mL of absolute ethyl alcohol, carrying out ultrasonic mixing in an ice-water bath for 15min, dropwise adding the mixture into a three-necked flask, reacting for 12h at 55 ℃, separating a product from a solution by using a strong magnet, washing for 3 times by using the absolute ethyl alcohol, and adding 5mL of absolute ethyl alcohol for dispersing to obtain the sulfhydrylation 3D graphene magnetic nanoparticles;
(3) preparation of catecholamine solid phase extraction functional composite material by adopting sulfydryl-alkene click chemical surface polymerization method
Placing 300-900 mg of sulfhydrylation 3D graphene magnetic nanoparticles into a three-neck flask, adding 50-150 mL of absolute ethyl alcohol, performing ultrasonic dispersion for 3min, stirring at 360rpm, and filling N2Taking 3-9 mmol of 2-phenyl acrylic acid, 0.0375-0.1125 g of azobisisobutyronitrile and 50-150 mL of absolute ethyl alcohol, dispersing by ultrasonic wave for 10min, dropwise adding into a three-necked flask, reacting for 2h at 65 ℃, reacting for 2h at 75 ℃, and using strong magnetism to reactSeparating the product from the solution by using iron, washing the solution for 3 times by using absolute ethyl alcohol, putting the obtained product into a filter paper cylinder, performing Soxhlet extraction for 2-6 h by using 100-300 mL of absolute ethyl alcohol as an eluent, removing impurities, and naturally drying the product to obtain the catecholamine solid phase extraction functional composite material.
4. The method for preparing catecholamine solid-phase extraction functional composite material as set forth in claim 3, characterized in that the Fe3O4The magnetic nano particles are prepared by adopting a chemical coprecipitation method according to the following steps: 10.6g of FeCl3·6H2O，4.0gFeCl2·4H2Placing O in a three-neck flask containing 200mL of deionized water, dissolving with ultrasound, starting stirring, introducing N2Deoxidizing, heating to 80 ℃, adding 25mL of strong ammonia water, reacting for 6h, separating the product from the solution by strong magnet, and washing Fe by deionized water3O4Adding 15mL of water to disperse until the solution is neutral to obtain black Fe3O4Magnetic nanoparticles.
5. The method for preparing catecholamine solid-phase extraction functional composite material according to claim 4, characterized in that the 3D graphene is prepared by the following steps: taking 10mL of graphene oxide with 2mg/mL, performing ultrasonic dispersion uniformly, sealing in a high-temperature reaction kettle with a 20mL polytetrafluoroethylene lining, reacting at 180 ℃ for 12h, cooling to room temperature, taking out the 3D graphene, sucking surface moisture with filter paper, and storing.
6. The use of the catecholamine solid phase extraction functional composite material of claim 1 in separating, enriching, purifying catecholamine substance residues in a sample.
7. Use of the catecholamine solid-phase extraction functional composite material as set forth in claim 1 in pretreatment for analysis of a cosmetic sample containing catecholamine substances.
8. The use according to claim 7, characterized by the following steps:
(1) activation of
Taking catecholamine solid phase extraction functional composite material 25mg, placing in a conical flask with a plug, activating with 3mL of methanol, discarding waste liquid, rinsing with 3mL of acetonitrile, removing methanol on the surface of the functional composite material, and discarding the waste liquid; then 3mL of acetonitrile is used for balancing, and waste liquid is discarded; obtaining the activated functional composite material;
(2) extraction of
Precisely weighing 0.5g of a cosmetic sample, placing the cosmetic sample in a centrifuge tube with a plug, accurately transferring 2mL of saturated sodium chloride solution and 10mL of acetonitrile, ultrasonically extracting for 10min in an ice water bath, centrifuging for 10min at 10000rpm at 4 ℃, accurately transferring 5mL of acetonitrile extract at the upper layer, adding the acetonitrile extract into the conical bottle with a plug in the step (1), and mixing the acetonitrile extract with the activated functional composite material; extracting under oscillation for 80min, separating with magnetic field, and discarding waste liquid;
(3) leaching with water
Leaching the functional composite material treated in the step (2) by using 3mL of acetonitrile, and discarding waste liquid;
(4) elution is carried out
Eluting the functional composite material by using 2-6 mL of 98:2 volume ratio 0.1% formic acid aqueous solution-methanol as an eluent, and collecting the eluent; blowing at 35 deg.C with nitrogen to obtain residue, dissolving the residue with 1mL eluent, filtering with 0.45 μm filter head, and analyzing by HPLC.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103709342A (en) * | 2013-12-23 | 2014-04-09 | 河北工业大学 | Preparation method of magnetic cadmium ion surface imprinted polymer |
| CN105312038A (en) * | 2014-07-29 | 2016-02-10 | 中国科学院大连化学物理研究所 | Formylphenylboronic acid modified magnetic nanoparticles and preparation and application thereof |
| JP2017023963A (en) * | 2015-07-24 | 2017-02-02 | 株式会社住化分析センター | Column packing material, separation method of column and enantiomers |
| CN107474254A (en) * | 2016-06-08 | 2017-12-15 | 中国科学院大连化学物理研究所 | The preparation and application of organic-inorganic hydrophilic hybrid integral material |
| CN107694539A (en) * | 2016-08-08 | 2018-02-16 | 中国人民解放军军事医学科学院放射与辐射医学研究所 | A kind of new anti-phase/weak cation exchange mixed mode chromatographic stationary phases and preparation method thereof |
-
2018
- 2018-04-04 CN CN201810304058.3A patent/CN108452784B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103709342A (en) * | 2013-12-23 | 2014-04-09 | 河北工业大学 | Preparation method of magnetic cadmium ion surface imprinted polymer |
| CN105312038A (en) * | 2014-07-29 | 2016-02-10 | 中国科学院大连化学物理研究所 | Formylphenylboronic acid modified magnetic nanoparticles and preparation and application thereof |
| JP2017023963A (en) * | 2015-07-24 | 2017-02-02 | 株式会社住化分析センター | Column packing material, separation method of column and enantiomers |
| CN107474254A (en) * | 2016-06-08 | 2017-12-15 | 中国科学院大连化学物理研究所 | The preparation and application of organic-inorganic hydrophilic hybrid integral material |
| CN107694539A (en) * | 2016-08-08 | 2018-02-16 | 中国人民解放军军事医学科学院放射与辐射医学研究所 | A kind of new anti-phase/weak cation exchange mixed mode chromatographic stationary phases and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| Optimizing Organic Functionality in Mesostructured Silica: Direct Assembly of Mercaptopropyl Groups in Wormhole Framework Structures;Yutaka Mori etal.;《Chem. Mater.》;20011231;第2173-2178页 * |
| 核－壳型磁性固相萃取材料对降糖保健品中甲苯磺丁脲吸附性能的研究;吴宗远等;《分析检测》;20161231;第49-59页 * |
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