CN109589931B - Magnetic covalent organic framework compound solid phase extraction adsorbent and preparation method thereof - Google Patents

Magnetic covalent organic framework compound solid phase extraction adsorbent and preparation method thereof Download PDF

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CN109589931B
CN109589931B CN201811480471.1A CN201811480471A CN109589931B CN 109589931 B CN109589931 B CN 109589931B CN 201811480471 A CN201811480471 A CN 201811480471A CN 109589931 B CN109589931 B CN 109589931B
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庞月红
岳琪
沈晓芳
杨成
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Abstract

The invention discloses a magnetic covalent organic framework compound magnetic solid phase extraction adsorbent and a preparation method thereof, belonging to the technical field of analytical chemistry and food safety detection. The invention provides a magnetic covalent organic framework compound solid phase extraction adsorbent and a preparation method thereof, wherein a Co-precipitation method is used for obtaining COF- (TpBD)/Fe by utilizing coordination of Fe ions and N atoms in TpBD3O4The mixture is used as adsorbent for extracting and purifying aromatic compounds in food matrix, especially phthalate target. The method simplifies the pretreatment process of the sample, synthesizes the magnetic adsorbent by using a coprecipitation method, is simple, quick and easy to obtain, reduces the extraction workload, and greatly reduces the detection limit of the phthalate compounds.

Description

Magnetic covalent organic framework compound solid phase extraction adsorbent and preparation method thereof
Technical Field
The invention relates to a magnetic covalent organic framework compound magnetic solid phase extraction adsorbent and a preparation method thereof, belonging to the technical field of analytical chemistry and food safety detection.
Background
The Magnetic Solid Phase Extraction (MSPE) adsorbent can be quickly dispersed and adsorbed in a sample solution, and can be quickly separated by using an external magnet. Compared with the traditional Solid Phase Extraction (SPE), MSPE has many obvious advantages, including easy operation, reduces the consumption of organic solvent, avoids SPE filler close packing and the high back pressure that arouses and quick simple outside magnet separation analyte, easily uses advantages such as usefulness with detecting instrument jointly. An important component of MSPE is the adsorbent material, which determines the sensitivity and selectivity of the process. Therefore, the Magnetic Solid Phase Extraction (MSPE) adsorbent having adsorption effect on PAEs is developed, and the adsorption performance can be improved.
Covalent Organic Frameworks (COFs) are a class of novel crystalline porous materials with highly ordered structures, composed of organic building blocks. COFs have many unique properties, such as permanent porosity and large specific surface area, which make COFs have great potential in the field of chromatography. However, its lower density makes its morphology often very dispersed, which affects its use. Thus, magnetizing it can combine the advantages of the MSPE, facilitating practical application of COF. COF @ Fe of core-shell structure is available3O4The material is used as a magnetic solid phase extraction adsorbent, but the synthesis process needs to be strictly controlled, so that the wide application of the material is limited. For example, Fe has been reported3O4The @ TpBD core-shell structure magnetic covalent-organic framework nanosphere needs to add tetraethyl orthosilicate (TEOS) and (3-aminopropyl) triethoxysilane (APTES) to introduce amino, then grow TpBD in situ, and the whole process needs to be strictly controlled; fe without amino modifier3O4The @ COF- (TpBD) core-shell structure nanosphere still needs to strictly control the synthesis process so as to ensure a better crystal form structure.
TpBD based on COF material has pi-pi conjugated system and rigid pore canal size
Figure BDA0001893251000000011
Chemical and thermal stability, etc. and is applied in the extraction analysis of target matter with aromatic structure. Taking into account the chemical structure and molecular size of the Phthalates (PAEs) (of the order of magnitude)
Figure BDA0001893251000000012
) Using the size selection effect of TpBD and pi-pi co-The maximum amount of Phthalic Acid Ester (PAEs) which cannot be brought into contact with grease food and infant food, di (α -ethylhexyl) phthalate (DEHP), diisononyl phthalate (DINP) and di-n-butyl phthalate (DBP) in food and food additives are specifically set in offices of the Ministry of health in China, and the maximum residual amounts of Phthalic Acid Ester (PAEs) in food and food additives are 1.5mg/kg, 9.0mg/kg and 0.3 mg/kg. respectively, so that the PAEs have attracted much attention to the development of contaminated food, and therefore, various practical and environmentally-friendly methods for rapid detection of phthalic acid ester have become necessary.
Disclosure of Invention
In order to solve the problems, the invention provides a magnetic covalent organic framework compound solid-phase extraction adsorbent and a preparation method thereof, and the adsorbent is applied to magnetic solid-phase extraction of phthalate. The invention synthesizes the novel magnetic solid phase extraction adsorbent rapidly and simply by coprecipitation and electrostatic adsorption, and the adsorbent has obvious enrichment effect on aromatic compounds based on the characteristics of large specific surface area, porosity, large pi-pi conjugated system and thermal stability of COF materials. At present, most of COF materials are magnetized by synthesizing core-shell structured nano materials, and the synthesis process needs to be strictly controlled. Therefore, it is one of the main points of the present invention to invent a method for magnetizing COFs easily and rapidly and separating and enriching aromatic compounds efficiently. The invention can be applied to the direct magnetic solid phase extraction of more complex matrixes and can be matched with gas chromatography or liquid chromatography detection.
The first purpose of the invention is to provide a preparation method of a novel magnetic solid phase extraction adsorbent, and the methodThe method realizes coprecipitation by using the combination of COF-TpBD and Fe ion coordination bonds, and comprises the following steps: placing COF-TpBD and an iron ion source in water, heating to 30-80 ℃, then adding ammonia water, and separating after complete reaction to obtain COF- (TpBD)/Fe3O4Magnetic solid phase extraction adsorbent.
In one embodiment of the invention, the ratio of COF- (TpBD) to the source of ferric ions is (0.04-0.12): 1, the iron ion source comprises a ferrous ion source and a ferric ion.
In one embodiment of the present invention, the mass ratio of the divalent iron ion source to the trivalent iron ion is 1: (1.5 to 3).
In one embodiment of the invention, the volume ratio of the aqueous ammonia to the aqueous solution is 3% to 10%.
In one embodiment of the invention, the mass ratio of the COF-TpBD to the iron ion source is (0.04-0.12): 1.
in one embodiment of the invention, the COF-TpBD has high crystallinity, a delocalized system, and good chemical stability.
In one embodiment of the invention, the method for synthesizing the COF-TpBD comprises the steps of utilizing a solvothermal method, an in-situ growth method, an ionothermal method, a microwave-assisted solvothermal method, a heating reflux method, a room-temperature solution method and the like.
In one embodiment of the invention, the process is a co-precipitation process, wherein COF- (TpBD) is combined with Fe3O4The mechanism of co-precipitation is to utilize the coordination bond between the N atom (having lone pair electrons) and the Fe ion (having vacant orbital) in COF- (TpBD).
In one embodiment of the invention, the source of divalent iron ions comprises one or more of its hydrochloride, sulfate, nitrate salts.
In one embodiment of the invention, the source of ferric ions comprises one or more of its hydrochloride, sulfate, nitrate salts.
In one embodiment of the present invention, the method specifically comprises:
(1) adding COF-TpBD and FeSO4·7H2O and FeCl3·6H2Mixing O with 150mL of water, and introducing nitrogen;
(2) uniformly stirring the mixed solution, heating to 30-80 ℃, adding 4.5-15 mL of ammonia water, and continuously stirring for 30-40 min;
(3) and after the solution is cooled, collecting the synthesized material by using an external magnet, washing the material by using deionized water and ethanol in sequence, and drying for later use.
In one embodiment of the invention, the COF-TpBD is synthesized by a solvothermal method, washed by acetone, tetrahydrofuran and ethanol, and dried.
The second purpose of the invention is to provide a novel magnetic solid phase extraction adsorbent COF- (TpBD)/Fe3O4。
A third object of the present invention is to provide a method for extracting or separating aromatic compounds, which comprises using the above-mentioned magnetic solid phase extraction adsorbent.
In one embodiment of the invention, the method comprises:
(1) according to the mass-to-volume ratio, adding COF- (TpBD)/Fe3O410-40 mg of the solution is added into 10-100 mL of solution of an object to be detected, and the solution is subjected to vortex oscillation for 15-50 minutes;
(2) COF- (TpBD)/Fe collected by magnetic force3O4And washing twice with pure water;
(3) then adding methanol or acetonitrile to elute COF- (TpBD)/Fe3O4An object of (1);
(4) COF- (TpBD)/Fe using an external magnet3O4Adsorbing on the container wall, and collecting the supernatant to obtain aromatic compound solution.
The extraction or separation principle is as follows: COF- (TpBD)/Fe3O4The COF- (TpBD) and the target are adsorbed by one or more of the selection effect of the pore channel size, the pi-pi conjugation effect and the hydrophobic acting force.
The fourth purpose of the invention is to provide a method for detecting aromatic compounds, which comprises the steps of pre-treating an object to be detected to obtain a sample, and then detecting the obtained sample; the pretreatment is carried out by using the magnetic solid phase extraction adsorbent.
In one embodiment of the invention, the detection comprises gas chromatography, or a combination of gas chromatography and mass spectrometry apparatus.
In one embodiment of the present invention, the aromatic compound is an aromatic compound having a benzene ring structure and a conjugated double bond structure and having a molecular weight of less than 1000 daltons, and includes a hydrocarbon group having C10 to C20, a hydrocarbon group having an aryl group, an ester group, an ether group, an amine group, an amide group, or a hydrophobic group such as an ester group.
A fifth object of the present invention is to provide a method for extracting phthalate ester compounds, which comprises:
(1) the magnetic solid phase extraction adsorbent COF- (TpBD)/Fe3O4Adding salt into the solution of the substance to be detected to obtain a mixed solution, and adsorbing;
(2) taking out COF- (TpBD)/Fe3O4Adding methanol or acetonitrile to elute and analyze, and separating to remove COF- (TpBD)/Fe3O4Thus obtaining the phthalate PAEs solution.
In one embodiment of the invention, COF- (TpBD)/Fe3O4The mass-volume ratio of the solution to be detected is (10-40): (10-100) mg/mL.
In one embodiment of the invention, the salt concentration in step (1) is from 0.5% to 1.5% w/v.
In one embodiment of the present invention, the adsorption time in step (1) is 5 to 45 min.
In one embodiment of the invention, the elution time in the step (2) is 2-25 min.
In one embodiment of the present invention, the pH of the mixed solution in the step (1) is 5.0 to 8.0.
The sixth purpose of the invention is to provide a method for detecting aromatic compounds, which comprises the steps of pre-treating an object to be detected to obtain a sample, and then detecting the obtained sample; the pretreatment is carried out by the extraction method.
Compared with the prior art, the invention has the following remarkable advantages:
(1) the preparation method of the magnetic adsorbent is simple, convenient and quick, and the obtained magnetic adsorbent has good solvent stability and can be repeatedly used for more than 5 times;
(2) the extraction separation method of the aromatic compound solves the problems that the traditional separation and enrichment method of the compound is easy to cause cross contamination and uses a large amount of organic solvent, does not need to use a large amount of organic solvent and vessels, and fully embodies the characteristic of environmental friendliness;
(3) the detection method of the aromatic compound simplifies the pretreatment process of the sample, is simple to operate, reduces the workload, has a good detection result, and has low detection limit and quantitative limit of various PAEs.
Drawings
FIG. 1 shows COF-TpBD and synthesis of Fe3O4Optimizing the feed ratio of equivalent raw materials;
FIG. 2 shows TpBD and Fe3O4、COF-(TpBD)/Fe3O4X-ray diffraction (XRD) pattern of (a);
FIG. 3 is Fe3O4And COF- (TpBD)/Fe3O4The hysteresis curve of (1);
FIG. 4 shows TpBD and Fe3O4、COF-(TpBD)/Fe3O4Fourier transform infrared (FT-IR) spectra of (A);
FIG. 5 is a diagram of optimization of the kind of extraction solvent;
FIG. 6 is an optimization plot of extraction solvent volume;
FIG. 7 is a graph of dose optimization of magnetic adsorbents;
FIG. 8 is an optimization plot of different solution sample volumes;
FIG. 9 is an optimization plot of extraction time;
FIG. 10 is an optimization plot of elution time;
FIG. 11 is an optimization plot of salt ion concentration;
FIG. 12 is a pH optimization chart.
Detailed description of the preferred embodiments
The invention is further described with reference to examples:
example 1: preparation of COF material-based magnetic solid phase extraction adsorbent
(1) Preparation of COF material: the stable covalent organic framework compound material is generated through solvothermal reaction. The selected COF material is COF-TpBD, and the raw materials used for synthesis are 63mg (0.3mmol) of trialdehyde phloroglucinol (Tp) and 48mg (0.45mmol) of Benzidine (BD). 3mL of mesitylene, 3mL of 1, 4-dioxane and 0.3mL of 6M acetic acid solution are used as organic solutions for synthesis. The materials are evenly mixed by ultrasonic wave and then transferred into a Teflon reaction kettle to react for 72 hours at 120 ℃. The material was taken out and washed repeatedly with acetone and dried under vacuum for further use.
(2) Magnetization of COF material: synthesis of COF- (TpBD)/Fe by coprecipitation3O4. Taking ferric chloride hexahydrate (FeCl)3·6H2O)0.4g, ferrous sulfate heptahydrate (FeSO)4·7H2O)0.25g, with appropriately ground COF-TpBD 35mg in a round-bottomed flask, and 100mL of pure water was added. Stirring the mixture evenly at 60 ℃ by using a Teflon stirring rod, adding 9mL of ammonia water, heating the mixture to 80 ℃, continuing stirring the mixture for 30min, and then cooling the mixture to room temperature. Washing the obtained material with pure water for 2-3 times, then washing with ethanol for 2-3 times, and drying in a vacuum drying oven for later use.
Characterization of the magnetic solid phase extraction adsorbent:
characterization of prepared TpBD, Fe by XRD3O4And COF- (TpBD)/Fe3O4Crystal structure and purity. As shown in FIG. 2, synthesized TpBD, COF- (TpBD)/Fe3O4The XRD pattern of the magnetic field was consistent with that of the simulation, indicating successful preparation and successful magnetization of TpBD. Fe3O4And COF- (TpBD)/Fe3O4The hysteresis curve of (2) is shown in fig. 3. Fe3O4And COF- (TpBD)/Fe3O4The saturation magnetization values of (a) are 61.1 and 51.8, respectively. Fe3O4And COF- (TpBD)/Fe3O4The relatively high saturation magnetization makes the adsorbent susceptible to magnetic fields and easy to separate from solution systems.
Confirmation of COF- (TpBD)/Fe by FT-IR Spectroscopy3O4Chemical composition and structure of the nanomaterial (fig. 4). COF- (TpBD)/Fe in comparison with the spectrum of COF- (TpBD)3O4Has a spectrum of 584cm-1An additional adsorption band is shown due to the Fe-O-Fe vibration of the magnetite. For COF- (TpBD), 1442cm-1The signal at (A) represents a characteristic stretch band of an aromatic C ═ C bond, the characteristic peaks of C-N stretch and C ═ N bond at 1292 and 1605cm, respectively-1This is because the synthesis reaction of TpBD involves a process of converting an enol structure into a ketone structure.
Example 2:
referring to example 1, the present invention used a one-factor test for COF-TpBD and synthetic Fe3O4The feeding ratio of the iron source raw material is optimized and investigated, as can be seen from fig. 1, the feeding ratio has more influence on the extraction and adsorption performance of the material, and the mass ratio is 0.04: 1 or less, the adsorption effect is generally poor and not more than 10%, 0.04: 1, the adsorption performance is gradually improved and reaches 0.12: 1, the adsorption effect of various compounds reaches 100 percent.
Example 3: using COF- (TpBD)/Fe3O4Extraction and detection of 15 PAEs in beverage sample
(1) Preparing a standard solution: PAEs-methanol standard solutions with a concentration of 1000mg/mL, comprising DMP/DEP/DIBP/DBP/DMEP/BMPP/DEEP/DPP/DHXP/BBP/DBEP/DCHP/DEHP/DphP/DNOP gradient dilutions to 100mg/mL, 10mg/mL, were used as stock and intermediate solutions, respectively. The standard curve working solution has the concentration of 5 mug/mL, 10 mug/mL, 20 mug/mL, 50 mug/mL, 100 mug/mL, 200 mug/mL, 500 mug/mL and 1000 mug/mL, and is prepared as before.
(2) Pretreatment of sample to be tested
Beer, carbonated beverages and alcoholic carbonated beverages are degassed in an ultrasonic bath to eliminate carbon dioxide. Then, drinks with more complicated bases such as milk drinks, fruit juices and milk tea are mixed with pure water at a ratio of 1: 8, and the other beverages were diluted with purified water at a ratio of 1: 5 to reduce matrix interference prior to the extraction process.
(3) Elimination of PAEs background
Since PAEs are widely available in many laboratory products, including chemicals and glassware, there may be a high background in the analysis of PAEs in real samples. To avoid PAEs contamination, all glassware used was washed with acetone or n-hexane and dried at 120 ℃ for at least 4h prior to use. All organic solvents used in the analytical experiments were of chromatographic grade. Organic solvents and plastic products that are inevitably used should first be analyzed by GC-MS to eliminate the possibility of PAEs contamination.
(4) Magnetic solid phase extraction
The method comprises the following specific steps: 1) 30mg of the material prepared in example 1 were taken in COF- (TpBD)/Fe3O4And added to 50mL of the spiked solution or sample solution. 2) After vortexing the solution, the COF- (TpBD)/Fe solution was vortexed using a powerful magnet3O4Collected and washed twice with pure water. 3) Then, desorption was carried out using 2mL of methanol, and COF- (TpBD)/Fe was eluted with shaking3O4The target object of (1). 4) COF- (TpBD)/Fe using an external magnet3O4Adsorbed on the vessel wall, all supernatants were collected and filtered through a 0.22 μm membrane to remove particulate matter prior to CG analysis, using GC analysis. Used COF- (TpBD)/Fe3O4Washing with methanol for three times, and recycling.
(1) The experiment uses gas chromatography-mass spectrometry for detection. The detection mode is a multiple reaction detection (MRM) mode. And recording a chromatogram, obtaining a peak area by integrating with self-contained software of a chromatograph, drawing a standard curve of 15 phthalic acid esters, and calculating to obtain the content of each phthalic acid ester in the sample to be detected.
TABLE 1 determination of the individual phthalates in the samples to be tested
Figure BDA0001893251000000061
Figure BDA0001893251000000071
Example 4:
the experiment optimizes and investigates the extraction conditions: the single-factor optimization experiments were conducted with reference to the conditions in example 1.
Two elution solvents (acetonitrile and methanol) were tested, setting different eluent volumes (0.5mL × 2, 1mL × 2, 2mL), amounts of magnetic adsorbent (10, 20, 30, 40mg), different sample solution volumes (10mL, 50mL, 100mL, 200mL), extraction times (5, 10, 20, 30, 40, 45min), elution times (2, 5, 10, 15, 20, 25min), salt ion concentrations (0, 0.3, 0.5, 1, 1.5% w/v) and pH values (5.0, 5.5, 6.0, 6.5, 7.0, 7.5, 8.0). As shown in fig. 5, 6, 7, 8, 9, 10, 11, and 12, the extraction conditions with good extraction effect are finally selected: 2mL of methanol as an elution solvent, 30mg of COF- (TpBD)/Fe3O4As an adsorbent, 30min was used as the extraction time and 15 min as the elution time, the salt ion concentration was 1% w/v, and the pH was 7.0.

Claims (10)

1. A preparation method of a magnetic solid phase extraction adsorbent is characterized in that the method realizes coprecipitation by combining an N atom with a lone pair electron in a covalent organic framework compound COF-TpBD and an Fe ion coordination bond with an empty orbit, and comprises the following steps: placing COF-TpBD and an iron ion source in water, heating to 30-80 ℃, then adding ammonia water, and separating after complete reaction to obtain COF-TpBD/Fe3O4Magnetic solid phase extraction adsorbent.
2. The method according to claim 1, wherein the mass ratio of the COF-TpBD to the source of ferric ions is (0.04-0.2): 1.
3. the method according to claim 1 or 2, wherein the iron ion source comprises ferrous ions and ferric ions, wherein the mass ratio of ferrous ions to ferric ions is 1: (1.5 to 3).
4. The method of claim 1, wherein the COF-TpBD/Fe is3O4Magnetic solid phase extraction adsorbent medium toolThe material with adsorption effect is TpBD, and the target object is adsorbed by utilizing one or more acting forces of pore channel size selection effect, pi-pi conjugated adsorption and hydrophobic property.
5. A magnetic solid phase extraction adsorbent, characterized in that the magnetic solid phase extraction adsorbent is prepared by the method of any one of claims 1 to 4.
6. A method for extracting aromatic compounds, which is characterized in that the method utilizes the magnetic solid phase extraction adsorbent of claim 5, and comprises the following steps:
(1) according to the mass-to-volume ratio, adding COF-TpBD/Fe3O410-40 mg of the reagent is added into 10-100 mL of solution of an object to be detected and mixed evenly;
(2) collecting COF-TpBD/Fe3O4Washing;
(3) then adding a solvent to elute COF-TpBD/Fe3O4The aromatic compound target of (1);
(4) separation to remove COF-TpBD/Fe3O4And collecting clear liquid to obtain the aromatic compound solution.
7. A method for extracting phthalate esters, the method comprising:
(1) the magnetic solid phase extraction adsorbent COF-TpBD/Fe as claimed in claim 53O40.5-1.5% w/v salt is added into the solution of the substance to be detected to obtain a mixed solution for adsorption;
(2) separating and taking out COF-TpBD/Fe3O4Adding methanol or acetonitrile for elution and analysis, and separating to remove COF-TpBD/Fe3O4Thus obtaining the phthalate PAEs solution.
8. The method of claim 7, wherein COF-TpBD/Fe3O4The mass-volume ratio of the solution to be detected is (10-40): (10-100) mg/mL.
9. The method according to claim 7 or 8, wherein the pH value of the mixed solution in the step (1) is 5.0 to 8.0.
10. The method for detecting the aromatic compound is characterized in that a sample is obtained by pretreating an object to be detected in advance, and then the obtained sample is detected; the pretreatment is carried out by using the magnetic solid phase extraction adsorbent according to claim 5 or the extraction separation method according to any one of claims 6 to 9.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107413313A (en) * 2017-07-18 2017-12-01 武汉大学 A kind of Magnetic solid phases extractant based on covalent organic framework material and its preparation method and application
CN108262019A (en) * 2018-02-11 2018-07-10 中国烟草总公司郑州烟草研究院 A kind of magnetism sulfonic functional COFs materials and its preparation method and application
CN108355613A (en) * 2018-03-02 2018-08-03 南京师范大学常州创新发展研究院 Magnetic covalent organic framework material and its preparation method and application

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107413313A (en) * 2017-07-18 2017-12-01 武汉大学 A kind of Magnetic solid phases extractant based on covalent organic framework material and its preparation method and application
CN108262019A (en) * 2018-02-11 2018-07-10 中国烟草总公司郑州烟草研究院 A kind of magnetism sulfonic functional COFs materials and its preparation method and application
CN108355613A (en) * 2018-03-02 2018-08-03 南京师范大学常州创新发展研究院 Magnetic covalent organic framework material and its preparation method and application

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Facile Synthesis of Magnetic Covalent Organic Framework with Three-Dimensional Bouquet-Like Structure for Enhanced Extraction of Organic Targets;Sijing He, et al.;《ACS Appl. Mater. Interfaces》;20170111;第9卷;第2959-2965页 *
Room-temperature synthesis of core–shell structured magnetic covalent organic frameworks for efficient enrichment of peptides and simultaneous exclusion of proteins;Guo Lin, et al.;《Chem. Commun.》;20170309;第53卷;第3649-3652页 *

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