CN113702538A - Magnetic porous carbon-based QuEChERS purification material and application thereof in sample pretreatment and tobacco pesticide residue detection - Google Patents
Magnetic porous carbon-based QuEChERS purification material and application thereof in sample pretreatment and tobacco pesticide residue detection Download PDFInfo
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Abstract
A magnetic porous carbon-based QuEChERS purification material and applications thereof in sample pretreatment and tobacco pesticide residue detection are provided, wherein the preparation method is to prepare magnetic Fe by adopting an ultrasonic-assisted reverse co-precipitation method3O4Nanoparticles based on magnetic Fe3O4Further preparation of Fe from nanoparticles3O4The method comprises the following steps of preparing a magnetic porous carbon-based QuEChERS purification material by taking the obtained composite material as a precursor and adopting a high-temperature calcination mode. The magnetic porous carbon-based QuEChERS purification material is used for replacing the purification material in the traditional QuEChERS sample pretreatment method, and most impurities can be removed by single use, so that the purification purpose is achieved, and the combination use of various purification materials is not needed; the purifying material has magnetic recovery performance, avoids multiple times of centrifugation in pretreatment, simplifies the pretreatment process and improves the analysis efficiency; the purifying material is applied to the pesticide residue detection of tobaccoWhen in measurement, the recovery rate and the precision are both better.
Description
Technical Field
The invention belongs to the technical field of pesticide residue detection, and particularly relates to a magnetic porous carbon-based QuEChERS purification material and application thereof in sample pretreatment and tobacco pesticide residue detection.
Background
The pesticide can prevent and control the invasion of diseases and pests to the tobacco, thereby improving the tobacco yield and quality. However, the use of a large amount of pesticide results in the residue of pesticide in tobacco. Since the pesticides to be analyzed and determined are often trace components in tobacco, and have various varieties and different chemical structures and properties, the complex tobacco matrix poses a great challenge to accurate quantitative detection of the tobacco matrix. QuEChERS (Quick-Easy-Cheap-Effective-Rugged-Safety) is a rapid sample pretreatment technology developed based on a solid phase extraction technology and a matrix solid phase dispersion technology, and the principle of the technology is that the interaction between a purification material and a matrix interferent is utilized to adsorb the interferent so as to achieve the purposes of impurity removal and purification. The key to realizing accurate detection of pesticide residues is to adopt QuEChERS purification materials to reduce matrix effect.
Currently, the most commonly used purification materials include N-propyl ethylenediamine (PSA), octadecylsilane bonded silica (C18), and Graphitized Carbon Black (GCB). PSA can remove more polar phenolic, carbohydrate and fatty acid matrix interferents by weak anion and polar interactions; c18 can remove less polar fatty acids, olefins, steroids, pigments, and oils and fats by nonpolar interactionA matrix disruptor; GCB with a planar structure can remove matrix interferents such as sterol and pigment through pi-pi interaction. On the basis, researchers develop novel QuEChERS purification materials, for example, the invention patent with the application number of 201810519826.7 discloses a magnetic hyperbranched polyamide-amine, the invention patent with the application number of 202010129744.9 discloses a magnetic fluorine-based multi-walled carbon nanotube, and the invention patent with the application number of 201810304789.8 uses graphene as the QuEChERS purification material. Since a single purifier material can only remove a certain class of matrix interferents, researchers have achieved a wider range of matrix interferent removal through the synergistic effect of two or more purifier materials. For example, the invention with the application number of 201210403627.2 uses a carbon material, a modified silica gel material and a magnetic ferroferric oxide composite material as purification materials, and the invention with the application number of 201710089362.6 uses C18, GCB and Fe3O4@SiO2@ PSA is a composite purification material. However, how to select two or more proper purification materials for combination still has certain blindness, and the dosage ratio of different purification materials needs to be optimized, so that the experimental process is very complicated. In addition, the disadvantage that the conventional purification material needs to be matched with the matrix limits the further application of the QuEChERS technology in pesticide residue detection. The main problems are that the adsorption capacity of the existing purifying material to the matrix interferents is not strong enough: on one hand, the active sites of the purification material are single, and only the matrix interferents with specific properties can be adsorbed and removed; on the other hand, the specific surface area of the purification material is limited, and two-dimensional materials such as graphene are easy to agglomerate in the actual use process, so that the actual specific surface area is sharply reduced.
Disclosure of Invention
The invention aims to provide a magnetic porous carbon-based QuEChERS purification material and application thereof in sample pretreatment and tobacco pesticide residue detection aiming at the existing problems.
In order to achieve the purpose, the invention provides the following technical scheme:
a magnetic porous carbon-based QuEChERS purification material is prepared by the following steps:
(1) magnetic Fe3O4Dispersing the nano particles in methanol to obtain a first solution; the magnetic Fe3O4The nano particles can be prepared by an ultrasonic-assisted reverse coprecipitation method, and can also be directly prepared from commercially available magnetic Fe3O4A nanoparticle product.
(2) Weighing a certain amount of metal ions and imidazole ligands, respectively dissolving in methanol to obtain a second solution and a third solution, adding the second solution into the first solution obtained in the step (1) under the condition of stirring at room temperature for reaction, adding the third solution into the reaction solution, and continuing the reaction;
(3) separating the precipitate obtained in the step (2) by an external magnetic field, washing and drying to obtain Fe3O4A MOFs composite material;
(4) fe obtained in the step (3)3O4the/MOFs composite material is used as a precursor, and the magnetic porous carbon-based QuEChERS purification material is prepared in a high-temperature calcination mode.
Further, the magnetic Fe prepared in the step (1)3O4The particle size range of the nano particles is 10-30 nm.
Further, the molar ratio of the metal ions to the imidazole ligands is 0.25, and the metal ions and Fe3O4The molar ratio of (A) to (B) is 0.1-5; the metal ions comprise cobalt ions, zinc ions, iron ions and copper ions; the imidazole ligands comprise imidazole, 2-methylimidazole, 2-ethylimidazole, 2-propylimidazole, 2-isopropylimidazole and benzimidazole.
Further, the high-temperature calcination is carried out in a nitrogen atmosphere, and the temperature of the high-temperature calcination is 300-900 ℃.
The invention also provides an application of the magnetic porous carbon-based QuEChERS purification material in sample pretreatment in tobacco pesticide residue detection. The specific application method comprises the following steps:
(1) soaking a tobacco sample in water, and mixing with acetonitrile to obtain a first mixed solution;
(2) adding sodium chloride, anhydrous magnesium sulfate, sodium citrate and disodium hydrogen citrate into the first mixed solution obtained in the step (1) and mixing to obtain a second mixed solution;
(3) mixing 1 mL of the second mixed solution obtained in the step (2) with anhydrous magnesium sulfate and the magnetic porous carbon-based QuEChERS purification material prepared by the invention to obtain a third mixed solution;
(4) separating the precipitate in the third mixed solution obtained in the step (3) by using an external magnetic field to obtain a supernatant;
(5) and (5) filtering the supernatant obtained in the step (4) by using a microporous filter membrane to obtain a sample solution for detection.
Further, the mass of the tobacco sample, the volume of water and the volume of acetonitrile in the step (1) are respectively 1-3 g, 5-15 mL and 5-15 mL.
Further, the mass ratio of the sodium chloride, the anhydrous magnesium sulfate, the sodium citrate and the disodium hydrogen citrate in the step (2) to the tobacco sample in the step (1) is 2-6: 0.5-1.5: 0.5-1.5: 0.25-0.75: 2.
further, the mass ratio of the anhydrous magnesium sulfate and the magnetic porous carbon-based QuEChERS purification material in the step (3) to the tobacco sample in the step (1) is 50-300: 5-15: 2000.
further, the mixing mode in the steps (1) - (3) is vortex, the speed of the vortex is 2000 rpm, and the time of the vortex is 1-5 min.
The invention also provides application of the magnetic porous carbon-based QuEChERS purification material in tobacco pesticide residue detection, wherein a sample is treated by the sample pretreatment method to obtain a solution to be detected; and analyzing the pesticide residue in the solution to be detected by adopting LC-Q-TOF MS.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the invention provides a magnetic porous carbon-based QuEChERS purification material and a preparation method thereof, wherein the magnetic porous carbon-based QuEChERS purification material is magnetic Fe3O4MOFs are grown on the surface of the nano-particles to obtain Fe3O4the/MOFs composite material is taken as a precursor and is calcined at high temperatureThe method for preparing the magnetic porous carbon-based QuEChERS purification material has the advantages that the MOFs with large specific surface area and uniform pore size distribution endows the magnetic porous carbon-based QuEChERS purification material with high specific surface area; porous carbon supported on Fe3O4The magnetic porous carbon-based QuEChERS purification material has high stability due to the surface of the nano particles, and the defect that the conventional two-dimensional purification material is easy to agglomerate in the actual use process is overcome; due to the existence of metal sites, nitrogen and other heteroatoms in MOFs, the magnetic porous carbon-based QuEChERS purification material has various active sites and can remove wider matrix interferents; magnetic Fe3O4The existence of the nano particles endows the purifying material with magnetic recovery performance, avoids multiple centrifugation in pretreatment, simplifies pretreatment process and improves analysis efficiency.
(2) The preparation method of the magnetic porous carbon-based QuEChERS purification material provided by the invention is simple, can realize batch amplification preparation, and can controllably adjust the properties of the magnetic porous carbon-based QuEChERS purification material by various simple methods according to requirements, such as adjusting the types and the dosage of metal ions and imidazole ligands, adjusting the calcination temperature and time, and the like.
(3) The sample pretreatment operation based on the magnetic porous carbon-based QuEChERS purification material is simpler, and the purification effect is better than that of the classical purification materials, such as PSA, C18 and GCB.
(4) When the magnetic porous carbon-based QuEChERS purification material provided by the invention is used for detecting the tobacco pesticide residues, the detection accuracy can be improved.
Drawings
FIG. 1 is a graph showing a comparison of the purification capacity of the purification materials in example 4 of the present invention and comparative examples 1 to 3.
Detailed Description
The following description will further describe embodiments of the present invention with reference to the accompanying drawings, but the present invention is not limited thereto.
Example 1
According to the document "Sono-assisted preparation of highly-effective peroxidase-like Fe3O4 magnetic nanoparticles for catalytic removal of organic pollutants with H2O2The method in Ultrason, Sonochem, 2010, 17: 526-3O4Nanoparticles dispersed in 50 mL of methanol to give a first solution (containing about 4 mmol of Fe)3O4) (ii) a 2.62 g of 2-methylimidazole (32 mmol) and 2.32 g of cobalt nitrate hexahydrate (8 mmol) were weighed out and dissolved in 50 mL of methanol to obtain a second solution and a third solution, respectively. The second solution was added to the first solution with stirring at room temperature. After reacting for 1 h, adding the third solution into the reaction solution, and continuing to react for 24 h. Collecting the precipitate by magnetic recovery, washing with water and methanol for several times, and drying in a vacuum drying oven at 35 deg.C to obtain Fe3O4A MOFs composite material. Mixing Fe3O4The MOFs composite material is placed in a tubular furnace in nitrogen atmosphere and calcined at 700 ℃, and the obtained product is the magnetic porous carbon-based QuEChERS purification material marked as Fe3O4@C。
Example 2
0.93 g of commercially available magnetic Fe was weighed3O4Nanoparticles (4 mmol), 3.53 g of 2-isopropylimidazole (32 mmol) and 2.38 g of zinc nitrate hexahydrate (8 mmol) were dissolved in 50 mL of methanol to give a first solution, a second solution and a third solution, respectively. The second solution was added to the first solution with stirring at room temperature. After reacting for 1 h, adding the third solution into the reaction solution, and continuing to react for 24 h. Collecting the precipitate by magnetic recovery, washing with water and methanol for several times, and drying in a vacuum drying oven at 35 deg.C to obtain Fe3O4A MOFs composite material. Mixing Fe3O4The MOFs composite material is placed in a tubular furnace in a nitrogen atmosphere and calcined at the temperature of 400 ℃, and the obtained product is the magnetic porous carbon-based QuEChERS purification material.
Example 3
According to the document "Sono-assisted preparation of highly-effective peroxidase-like Fe3O4 magnetic nanoparticles for catalytic removal of organic pollutants with H2O2. Ultrason. Sonochem. 2010, 17:526-533' method for preparing magnetic Fe by using ultrasonic-assisted reverse coprecipitation method3O4Nanoparticles dispersed in 50 mL of methanol to give a first solution (containing about 4 mmol of Fe)3O4) (ii) a 2.62 g of 2-methylimidazole (32 mmol) and 2.38 g of zinc nitrate hexahydrate (8 mmol) were weighed out and dissolved in 50 mL of methanol to obtain a second solution and a third solution, respectively. The second solution was added to the first solution with stirring at room temperature. After reacting for 1 h, adding the third solution into the reaction solution, and continuing to react for 24 h. Collecting the precipitate by magnetic recovery, washing with water and methanol for several times, and drying in a vacuum drying oven at 35 deg.C to obtain Fe3O4A MOFs composite material. Mixing Fe3O4The MOFs composite material is placed in a tubular furnace in a nitrogen atmosphere and calcined at 900 ℃, and the obtained product is the magnetic porous carbon-based QuEChERS purification material.
Example 4
The application of the magnetic porous carbon-based QuEChERS purification material prepared in the embodiment 1 in sample pretreatment in tobacco pesticide residue detection comprises the following specific operation steps:
weighing about 2.00 g of blank tobacco powder sample into a 50 mL centrifuge tube with a plug, adding 10 mL of water, shaking until the sample is fully soaked, standing for 10 min, adding 10 mL of acetonitrile into the centrifuge tube, and placing on a vortex mixer to shake for 2 min at 2000 rpm. The centrifuge tube was frozen in a freezer at-20 ℃ for 10 min. Then 4 g of anhydrous magnesium sulfate, 1g of sodium chloride, 1g of sodium citrate and 0.5 g of disodium hydrogen citrate are added into the centrifuge tube in sequence, the centrifuge tube is immediately placed on a vortex mixer to be shaken for 2 min at the speed of 2000 rpm so as to prevent the anhydrous magnesium sulfate from reacting with water to cause local overheating and caking, and the centrifuge tube is centrifuged for 3 min at 5000 rpm. Taking 1 mL of the supernatant into a 2 mL centrifuge tube, adding 150 mg of anhydrous magnesium sulfate and 10 mg of Fe3O4@ C, after oscillating for 2 min on the vortex mixer, placing the magnet side to realize separation, and filtering the supernatant with a membrane to be measured.
Comparative example 1
Fe in the purification process of example 43O4The @ C is replaced by PSA and the separation realized by placing the side of the magnet is replaced by centrifuging at 14000 rpm for 10 minOtherwise, the procedure was as in example 4.
Comparative example 2
The procedure was as in comparative example 1 except that the purification material was C18.
Comparative example 3
The same as in comparative example 1 except that the purification material was GCB.
The purification capacity of the purification materials in example 4 and comparative examples 1 to 3 was evaluated by the evaporation residue gravimetric method, which specifically comprises: and (3) putting 0.5 mL of purified supernatant into a clean test tube weighed in advance, blowing and drying the test tube by using nitrogen, putting the test tube into a 110 ℃ drying oven for 1 h, taking the test tube out, putting the test tube into a dryer for cooling, and weighing, wherein the difference of the two weighing is the amount of the co-extraction matrix. As shown in figure 1, the magnetic porous carbon-based QuEChERS purification material (Fe) prepared by the invention3O4@ C) is superior to classical QuEChERS purifier material PSA, and significantly superior to traditional purifier materials GCB and C18.
Example 5
The application of the magnetic porous carbon-based QuEChERS purification material prepared in the embodiment 1 in tobacco pesticide residue detection.
The pretreatment method based on the magnetic porous carbon-based QuEChERS purification material in the embodiment 4 is used for detecting the tobacco pesticide residues, and the LC-Q-TOF MS is adopted to analyze the pesticide residues in the solution to be detected.
The chromatographic conditions of LC-Q-TOF MS analysis are as follows: chromatography column, Atlantis @ T3 column (column length 150 mm, internal diameter 2.1 mm, stationary phase particle 3 μm); column temperature, 40 ℃; flow rate, 0.2 mL/min; sample size, 10 μ L; mobile phase a, 0.1% formic acid in ammonium acetate (5 mmol/L); mobile phase B, acetonitrile; elution gradient, 0-1 min, 10% -50% B; 1-5 min, 50% B; 5-16 min, 50% -60% B; 16-25 min, 60% -80% B; 25-30 min, 80% -95% B; 30-40 min, 95% B; 40-40.1 min, 95-10% B; 40.1-50.1 min, 10% B. The mass spectrum conditions are as follows: ion source, ESI; the scanning range is 100-1000 m/z; electrospray voltage, 5500V; atomization gas pressure, 0.38 MPa (55 psi); air curtain pressure, 0.24 MPa (35 psi); auxiliary air pressure, 0.34 MPa (50 psi); ion source temperature, 500 ℃; cluster cleavage voltage (DP), 40V; collision Energy (CE), 10V; scanning mode, positive ion scanning; monitoring mode, information association acquisition mode (IDA).
When the LC-Q-TOF MS is adopted to analyze the pesticide residue in the solution to be detected, a working curve of the pesticide to be detected needs to be made first.
The working curve of the pesticide is prepared as follows:
10.0 mg of triphenyl phosphate (TPP) standard substance is accurately weighed and placed in a 10 mL volumetric flask, diluted by acetonitrile and subjected to constant volume to obtain internal standard stock solution with the concentration of 1000 mug/mL. And (3) transferring 1.0 mL of the internal standard stock solution into a 100 mL volumetric flask, diluting with acetonitrile and fixing the volume to obtain an internal standard solution with the concentration of 10 mu g/mL. 0.01 g (accurate to 0.0001 g) of each pesticide standard substance is weighed in a 10 mL volumetric flask respectively, diluted by acetonitrile to a constant volume, and prepared into a single stock standard solution of 1000 mug/mL. And (3) transferring 0.5 mL of the single standard stock solution of each pesticide into a 100 mL volumetric flask, and fixing the volume to a scale by using acetonitrile to prepare a mixed standard working solution (5 mu g/mL) of each pesticide. The mixed standard working solution with the concentration of 5 mug/mL is diluted by acetonitrile to obtain series of standard solutions with the concentrations of 2, 5, 10, 20, 50, 100 and 200 ng/mL (0.5 mL of 10 mug/mL internal standard solution is added into each volumetric flask, and the concentration of the internal standard solution is 20 ng/mL). Taking 0.5 mL of the blank sample extracting solution purified in the embodiment 4, blowing nitrogen to be dry, and re-dissolving by using 0.5 mL of series standard solutions respectively to obtain series of matrix matching standard solutions with the concentrations of 2, 5, 10, 20, 50, 100 and 200 ng/mL respectively. LC-Q-TOF MS is adopted to measure the series of matrix matching standard solutions, a working curve of each pesticide is drawn, and relevant performance parameters of the tobacco pesticide residue detection method are obtained and comprise the working curve, a linear correlation coefficient, a detection limit and a quantification limit, and the parameters are shown in a table 1.
Table 1 relevant parameters for each pesticide detection method.
Example 6
The mixed pesticide working solution with different mass concentration levels of low, medium and high is respectively added into a blank tobacco sample to respectively prepare a standard adding sample of 0.02, 0.05 and 0.2 mg/kg. The spiked samples were treated according to the pretreatment method in example 4, and after pretreatment of the samples, the pesticides in the solution to be tested were analyzed by the LC-Q-TOF MS method in example 5, and then the concentrations of the pesticides were calculated according to the working curves prepared in example 5, and the spiked recovery rate was calculated, and repeated 6 times for each level. The recovery and Relative Standard Deviation (RSD) are shown in Table 2.
TABLE 2 recovery of the pesticides normalized to their relative standard deviation
As can be seen from the data in Table 2, when the pretreatment method provided by the invention is used for detecting the standard-added sample, the average recovery rate is 80.8-113.3%, and the RSD is not more than 16.3%. Therefore, the detection method established by the pretreatment method provided by the invention has better recovery rate and precision.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (16)
1. A magnetic porous carbon-based QuEChERS purification material is characterized by being prepared by the following method steps:
(1) magnetic Fe3O4Dispersing the nano particles in methanol to obtain a first solution;
(2) weighing a certain amount of metal ions and imidazole ligands, respectively dissolving in methanol to obtain a second solution and a third solution, adding the second solution into the first solution obtained in the step (1) under the condition of stirring at room temperature for reaction, adding the third solution into the reaction solution, and continuing the reaction;
(3) separating the precipitate obtained in the step (2) by an external magnetic field, washing and drying to obtain Fe3O4A MOFs composite material;
(4) fe obtained in the step (3)3O4the/MOFs composite material is used as a precursor, and the magnetic porous carbon-based QuEChERS purification material is prepared in a high-temperature calcination mode.
2. The magnetic porous carbon-based QuEChERS purification material of claim 1, wherein the magnetic Fe3O4The nano particles are prepared by an ultrasonic-assisted reverse coprecipitation method.
3. The magnetic porous carbon-based QuEChERS purification material of claim 1, wherein the metal ions comprise cobalt ions, zinc ions, iron ions and copper ions.
4. The magnetic porous carbon-based QuEChERS purification material according to claim 1, wherein the imidazole-based ligand comprises imidazole, 2-methylimidazole, 2-ethylimidazole, 2-propylimidazole, 2-isopropylimidazole and benzimidazole.
5. The magnetic porous carbon-based QuEChERS purification material according to claim 1 or 2, wherein the magnetic Fe3O4The particle size range of the nano particles is 10-30 nm.
6. The magnetic porous carbon-based QuEChERS purification material as claimed in claim 1, wherein the molar ratio of the metal ions to the imidazole ligands is 0.25, and the metal ions to Fe3O4The molar ratio of (A) to (B) is 0.1-5.
7. The magnetic porous carbon-based QuEChERS purification material according to claim 1, wherein the high temperature calcination is performed in a nitrogen atmosphere.
8. The magnetic porous carbon-based QuEChERS purification material according to claim 1 or 7, wherein the temperature of the high-temperature calcination is 300-900 ℃.
9. Use of a magnetic porous carbon-based QuEChERS purification material according to any one of claims 1-8 in sample pretreatment in tobacco pesticide residue detection.
10. The use according to claim 9, wherein the method of application in the pre-treatment of the sample comprises the steps of:
(1) soaking a tobacco sample in water, and mixing with acetonitrile to obtain a first mixed solution;
(2) adding sodium chloride, anhydrous magnesium sulfate, sodium citrate and disodium hydrogen citrate into the first mixed solution obtained in the step (1) and mixing to obtain a second mixed solution;
(3) mixing 1 mL of the second mixed solution obtained in the step (2) with anhydrous magnesium sulfate and the magnetic porous carbon-based QuEChERS purification material of claims 1-8 to obtain a third mixed solution;
(4) separating the precipitate in the third mixed solution obtained in the step (3) by using an external magnetic field to obtain a supernatant;
(5) and (5) filtering the supernatant obtained in the step (4) by using a microporous filter membrane to obtain a sample solution for detection.
11. The use according to claim 10, wherein the mass of the tobacco sample, the volume of water and the volume of acetonitrile in step (1) are 1-3 g, 5-15 mL and 5-15 mL, respectively.
12. The use according to claim 10, wherein the mass ratio of the sodium chloride, the anhydrous magnesium sulfate, the sodium citrate and the disodium hydrogen citrate in the step (2) to the tobacco sample in the step (1) is 2-6: 0.5-1.5: 0.5-1.5: 0.25-0.75: 2.
13. the use of claim 10, wherein the mass ratio of the anhydrous magnesium sulfate and the magnetic porous carbon-based QuEChERS purification material in the step (3) to the tobacco sample in the step (1) is 50-300: 5-15: 2000.
14. the use according to claim 10, wherein the mixing in steps (1) - (3) is performed by vortexing at 2000 rpm for 1-5 min.
15. Use of a magnetic porous carbon-based QuEChERS purification material according to any one of claims 1-8 in tobacco pesticide residue detection.
16. The application of the tobacco pesticide residue detection method in the claim 15, is characterized by comprising the following steps: treating a sample by using the sample pretreatment method according to any one of claims 10 to 14 to obtain a solution to be tested; and analyzing the pesticide residue in the solution to be detected by adopting LC-Q-TOF MS.
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| AMIRHASSAN AMIRI 等: "Synthesis of a zinc-based metal-organic framework with histamineas an organic linker for the dispersive solid-phase extraction oforganophosphorus pesticides in water and fruit juice samples", 《JOURNAL OF CHROMATOGRAPHY A》 * |
| 杨晓涵 等: "磁性金属有机骨架-聚多巴胺的制备并用于水产养殖水样中阳离子染料的萃取检测", 《色谱》 * |
| 董南巡 等: "磁固相萃取-高效液相色谱-串联质谱法测定环境水样中的苯脲类除草剂残留", 《理化检验(化学分册)》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114324683A (en) * | 2021-12-17 | 2022-04-12 | 南通市疾病预防控制中心 | High-throughput determination method and application of bisphenol and halogenated derivatives thereof in food |
| CN115770559A (en) * | 2022-12-09 | 2023-03-10 | 华侨大学 | Cerium metal organic framework magnetic material and preparation method and application thereof |
| CN115770559B (en) * | 2022-12-09 | 2024-03-15 | 华侨大学 | Cerium metal organic framework magnetic material and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113702538B (en) | 2023-05-12 |
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