CN114487083B - Magnetic hydroxyl nano material Fe3O4@COFs and application thereof in field of sulfanilamide mass spectrum detection - Google Patents
Magnetic hydroxyl nano material Fe3O4@COFs and application thereof in field of sulfanilamide mass spectrum detection Download PDFInfo
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- CN114487083B CN114487083B CN202210065335.6A CN202210065335A CN114487083B CN 114487083 B CN114487083 B CN 114487083B CN 202210065335 A CN202210065335 A CN 202210065335A CN 114487083 B CN114487083 B CN 114487083B
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 title claims abstract description 28
- 238000001514 detection method Methods 0.000 title claims abstract description 23
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- 238000001819 mass spectrum Methods 0.000 title description 8
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 title description 5
- FDDDEECHVMSUSB-UHFFFAOYSA-N sulfanilamide Chemical compound NC1=CC=C(S(N)(=O)=O)C=C1 FDDDEECHVMSUSB-UHFFFAOYSA-N 0.000 title description 4
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- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
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- WXTMDXOMEHJXQO-UHFFFAOYSA-N 2,5-dihydroxybenzoic acid Chemical compound OC(=O)C1=CC(O)=CC=C1O WXTMDXOMEHJXQO-UHFFFAOYSA-N 0.000 description 2
- QPVSSARHYZXAPM-UHFFFAOYSA-N 2-amino-2-oxoethanesulfonic acid Chemical class NC(=O)CS(O)(=O)=O QPVSSARHYZXAPM-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
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- 238000010521 absorption reaction Methods 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
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- SEEPANYCNGTZFQ-UHFFFAOYSA-N sulfadiazine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)NC1=NC=CC=N1 SEEPANYCNGTZFQ-UHFFFAOYSA-N 0.000 description 2
- 229960004306 sulfadiazine Drugs 0.000 description 2
- 229960002135 sulfadimidine Drugs 0.000 description 2
- JNMRHUJNCSQMMB-UHFFFAOYSA-N sulfathiazole Chemical compound C1=CC(N)=CC=C1S(=O)(=O)NC1=NC=CS1 JNMRHUJNCSQMMB-UHFFFAOYSA-N 0.000 description 2
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- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 description 2
- BLGVGDQFSHMDSK-UHFFFAOYSA-N 1,2-oxazole-3-sulfonic acid Chemical class [O-]S(=O)(=O)C=1C=CO[NH+]=1 BLGVGDQFSHMDSK-UHFFFAOYSA-N 0.000 description 1
- 101710120910 2,3-dihydroxybenzoate decarboxylase Proteins 0.000 description 1
- ZGDMDBHLKNQPSD-UHFFFAOYSA-N 2-amino-5-(4-amino-3-hydroxyphenyl)phenol Chemical compound C1=C(O)C(N)=CC=C1C1=CC=C(N)C(O)=C1 ZGDMDBHLKNQPSD-UHFFFAOYSA-N 0.000 description 1
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- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
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- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
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- AFVLVVWMAFSXCK-UHFFFAOYSA-N α-cyano-4-hydroxycinnamic acid Chemical compound OC(=O)C(C#N)=CC1=CC=C(O)C=C1 AFVLVVWMAFSXCK-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention belongs to the technical field of magnetic adsorption materials, and particularly relates to a magnetic hydroxyl nano material Fe 3O4 @COFs, and further discloses application of the magnetic hydroxyl nano material Fe 3O4 @COFs in preparation of a sulfonamide mass spectrometry detection probe. The magnetic hydroxyl nano material Fe 3O4 @COFs takes monodisperse Fe 3O4 nano particles as cores and TAPB and DHTP as monomers, and the hydroxyl-rich core-shell structure magnetic covalent organic framework nanospheres are rapidly synthesized at room temperature. The Fe 3O4 @COFs nano material has the advantages of average pore size distribution, high magnetization intensity, high specific surface area, good chemical stability, optical absorptivity and the like, the rich hydroxyl groups of the Fe 3O4 @COFs nano material can form hydrogen bonds with amino groups of sulfonamide antibiotic molecules, pi-pi conjugation acting force is formed between the surface of the COFs and benzene rings of the sulfonamide, and the magnetic core can realize rapid separation of samples, is an adsorbent for rapidly enriching and separating the sulfonamide, and simultaneously is used as a matrix for matrix-assisted laser analysis ionization mass spectrometry analysis, has lower background interference when measuring sulfonamide low-molecular targets, can effectively absorb laser energy and promote ionization of the targets, so that the sulfonamide low-molecular targets become ideal MALDI matrix materials.
Description
Technical Field
The invention belongs to the technical field of magnetic adsorption materials, in particular relates to a magnetic hydroxyl nano material Fe 3O4 @COFs, and more particularly relates to a magnetic hydroxyl organic framework nano material Fe 3O4 @COFs with a core-shell structure, and further discloses application of the magnetic hydroxyl nano material Fe 3O4 @COFs in preparation of a sulfonamide matrix assisted laser desorption ionization mass spectrometry detection probe.
Background
Sulfonamide antibiotics are emerging organic pollutants in water environments and foods, and the residue of the sulfonamide antibiotics can cause bacteria to generate drug resistance genes for antibiotics, thereby forming a potential threat to human and ecological system health. In general, detection of sulfonamide antibiotics remains a significant challenge due to the complexity of the matrix and low levels of sulfonamide antibiotics in the environment (tap water, surface water, groundwater and environmental waste water) and biological samples (milk, pork, fish). At present, the traditional method for analyzing the sulfonamide compound in the complex sample mainly depends on a High Performance Liquid Chromatography (HPLC) tandem mass spectrometry (MS/MS) or a spectrophotometry detector, but the method has the defects of complex sample preparation process, time and labor waste. Therefore, establishing a simple, rapid and accurate method for monitoring sulfonamide antibiotics in complex substrates and food products in the environment has attracted great attention to researchers in the field of food safety.
The matrix-assisted laser desorption ionization mass spectrometry is a rapid and convenient method capable of meeting high-throughput analysis, provides a powerful tool for high-throughput analysis of macromolecules (such as proteins, polypeptides, polymers and the like), and is applied to analysis and detection of sulfonamide antibiotics, thereby being a great breakthrough in the detection of sulfonamide antibiotics. The conventional matrix for matrix-assisted laser desorption ionization mass spectrometry is generally a conventional organic matrix, but when the conventional organic matrix is used for analyzing a compound with a molecular weight of less than 600Da, background interference is often caused to influence a detection result, so that the development of the matrix with small background interference becomes a key link for establishing the analysis method.
With the rapid development of nanomaterial technology, various nanomaterials have been developed, such as porous silicon, metal/metal oxide nanoparticles, carbon nanotubes, graphene, quantum dots, metal-organic framework nanomaterials, and the like, as potential matrix materials for MALDI-TOF mass spectrometry, in an attempt to solve this problem. Among them, covalent organic framework materials have been applied in MALDI-TOF mass spectrometry and achieve good results due to their large specific surface area, porous structure, good chemical stability and pi-pi stacking interactions. The synthesized boric acid functionalized covalent organic frameworks such as Zhao Shulin are used for enriching and directly detecting specific cis-diol compounds, and the synthesized Fe 3O4 @COFs can realize rapid solid-liquid separation under the help of an external magnetic field, so that the great advantages of COFs separation and enrichment are increased. For example, in the group of fomentation and Cai Zongwei, 1,3, 5-trialdehyde Benzene (BTA) and 3,3' -dihydroxybenzidine (DHBD) are used as monomers to synthesize Fe 3O4 @COFs in tetrahydrofuran, and the Fe 3O4 @COFs is used for analyzing polycyclic aromatic hydrocarbon in PM2.5 by using matrix-assisted laser desorption ionization mass spectrometry; fe 3O4 @COFs were synthesized from 1,3, 5-tris (4-aminophenyl) benzene (TAPB) and Terephthalaldehyde (TPA) in dimethylsulfoxide solvent and used for bisphenol A in pharmaceuticals and personal care products.
However, the advantages of the Fe 3O4 @cofs nanomaterial as an MS probe of a dual-function platform for high-throughput screening of dangerous compounds in a sample still need to be further demonstrated, and meanwhile, designing and developing a simple synthesis method for magnetizing COFs to enrich low-abundance target molecules by using different monomers is still a challenge, so that the Fe 3O4 @cofs nanomaterial still needs to be further explored in the new research field.
The information disclosed in this background section is only for enhancement of understanding of the general background of the invention and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person of ordinary skill in the art.
Disclosure of Invention
The invention aims to provide a magnetic hydroxyl organic framework nano material Fe 3O4 @COFs with a core-shell structure, wherein the Fe 3O4 @COFs nano material is rich in hydroxyl groups, can form a hydrogen bond with amino groups of sulfonamide antibiotic molecules, and the surface of the COFs and a benzene ring of sulfonamide form pi-pi conjugation, so that a magnetic core can realize rapid separation of a sulfonamide sample, and simultaneously is used as a matrix for matrix-assisted laser analysis ionization mass spectrometry analysis, and has lower background interference when measuring a sulfonamide low-molecular target object, can effectively absorb laser energy and promote ionization of the target object, so that the magnetic hydroxyl organic framework nano material becomes an ideal MALDI matrix material;
the invention also aims to provide the application of the Fe 3O4 @COFs nano material in preparing a sulfonamide mass spectrometry detection probe.
In order to solve the technical problems, the preparation method of the magnetic hydroxyl nano material Fe 3O4 @COFs comprises the step of carrying out synthesis reaction by taking Fe 3O4, 1,3, 5-tris (4-aminophenyl) benzene (TAPB) and 2,5, dihydroxyterephthalaldehyde (DHTP) as monomers in a solvent system.
Specifically, the molar ratio of 1,3, 5-tris (4-aminophenyl) benzene (TAPB) to 2,5, dihydroxyterephthalaldehyde (DHTP) is 1:1-2, and preferably in a molar ratio of 2:3.
Specifically, the mass ratio of Fe 3O4 to TAPB to DHTP is 50-100:15:10, preferably the mass ratio is 100:15:10 or 50:15:10; or 75:15:10.
Specifically, the temperature of the synthesis reaction is room temperature, the reaction time is 48-120h, and the reaction is preferably 72h.
Specifically, the method further comprises the steps of collecting the reaction product for washing, centrifuging and drying.
The invention also discloses a magnetic hydroxyl nano material Fe 3O4 @COFs with a core-shell structure prepared by the method.
The invention also discloses application of the magnetic hydroxyl nano material Fe 3O4 @COFs in the field of rapid analysis and detection of Sulfonamide Antibiotics (SAs) by an auxiliary matrix laser desorption ionization mass spectrometry (MALDI MS) technology.
The invention also discloses a method for rapidly analyzing and detecting the Sulfonamide Antibiotics (SAs) based on an auxiliary matrix laser desorption ionization mass spectrometry (MALDI MS) technology, which comprises the step of detecting the sulfonamide antibiotics in a sample to be detected by taking the magnetic hydroxyl nano material Fe 3O4 @COFs as a matrix.
Specifically, the sample to be measured comprises an environmental water sample, a milk sample or a meat sample.
The invention also discloses application of the magnetic hydroxyl nano material Fe 3O4 @COFs in preparing a sulfonamide mass spectrometry detection probe.
The magnetic hydroxyl nano material Fe 3O4 @COFs takes monodisperse Fe 3O4 nano particles as cores, takes 1,3, 5-tri (4-aminophenyl) benzene (TAPB) and 2,5, dihydroxyterephthalaldehyde (DHTP) as monomers, and rapidly synthesizes the hydroxyl-enriched core-shell structure magnetic covalent organic framework nanospheres at room temperature. The Fe 3O4 @COFs nano material has the advantages of average pore size distribution (4.3 nm), high magnetization intensity (40.2 emu g -1), high specific surface area (156 m 2g-1), good chemical stability, optical absorptivity and the like, and abundant hydroxyl groups can form hydrogen bonds with sulfonamide antibiotics, the surface of the COFs and the benzene ring of sulfonamide form pi-pi conjugation, so that the rapid separation of a sample can be realized, and the nano material is an adsorbent for rapidly enriching and separating sulfonamide, so that the nano material becomes an ideal MALDI matrix material.
The invention uses the magnetic hydroxyl nano material Fe 3O4 @COFs for assisting a matrix laser analysis ionization mass spectrometry (MALDI MS) technology to rapidly analyze the Sulfonamide Antibiotics (SAs) in the environmental water for the first time, and the magnetic hydroxyl nano material Fe 3O4 @COFs which is used as a matrix is applied to MALDI MS analysis of sulfonamide molecules has the advantages of high ionization efficiency, small fragment interference, good reproducibility, good salt tolerance and the like; the method is used for MALDI-TOF mass spectrometry analysis of 6 sulfonamide antibiotics, also shows good enrichment and ionization advantages, and fully proves the advantages of wide applicability, strong salt tolerance, good reproducibility and high sensitivity. The scheme of the invention further expands the application range of core-shell Fe 3O4 @COFs, is not only suitable for environmental water samples, but also is used for sample analysis of milk, pork and fish, achieves good effects, and provides a rapid analysis method for small molecule detection of sulfonamides.
Drawings
FIG. 1a is a scanning electron microscope of Fe 3O4; b is a scanning electron microscope image of Fe 3O4 @COFs; c is a transmission electron microscope image of Fe 3O4; d is a transmission electron microscope image of Fe 3O4 @COFs;
XPS for Fe 3O4 @ COFs in FIG. 2; b is the hysteresis curve of Fe 3O4 @ COFs; c is an infrared spectrogram of Fe 3O4 and Fe 3O4 @COFs; d is the adsorption-desorption and pore size distribution diagram of Fe 3O4 @COFs;
A in FIG. 3 is a blank mass spectrum of Fe 3O4 @ COFs; b-f are mass spectrograms of Fe 3O4 @ COFs, HCCA, DHB, graphene and Fe 3O4 serving as matrixes for detecting the sulfonamide antibiotics;
FIG. 4 is a mass spectrum of a salt tolerance investigation of Fe 3O4 @ COFs against NaCl of different concentrations, wherein the sulfoacetamides: 5ng/mL;
in FIG. 5, a-c are the results of the influence of the Fe 3O4 @COF amount, pH value and extraction time on the signal intensity of the sulfonamide molecule mass spectrum respectively;
FIG. 6 is a linear equation for different sulfonamide molecules;
In FIG. 7, a-c are mass spectra of a blank water sample, a sulfonamide sample with a standard of 0.1ng/mL, and a Fe 3O4 @COF enriched blank water sample with a standard of 0.1 ng/mL.
Detailed Description
The following detailed description of embodiments of the invention is, therefore, to be taken in conjunction with the accompanying drawings, and it is to be understood that the scope of the invention is not limited to the specific embodiments.
Throughout the specification and claims, unless explicitly stated otherwise, the term "comprise" or variations thereof such as "comprises" or "comprising", etc. will be understood to include the stated element or component without excluding other elements or components.
Example 1 Fe 3O4 Synthesis of COFs
Fe 3O4 (100 mg, synthesized according to the prior art), TAPB (0.04 mmol) and DHTP (0.06 mmol) were placed in a 50mL single-port bottle, and then 5mL acetonitrile was added thereto, and the above mixture was sonicated for 1min in order to sufficiently mix and disperse the above materials; then 0.4mL of acetic acid (12M) was added, the mixture was shaken well, and the reaction was carried out at room temperature for 72h; the resulting brown yellow solid was collected, washed with 25mL of methanol, centrifuged at 8000rpm/min for 10 minutes, washed and centrifuged three times, and dried under vacuum at room temperature overnight.
Example 2 Fe 3O4 Synthesis of COFs
Fe 3O4 (75 mg, synthesized according to the prior art), TAPB (0.04 mmol) and DHTP (0.06 mmol) were placed in a 50mL single-port bottle, and then 5mL acetonitrile was added thereto, and the above mixture was sonicated for 1min in order to sufficiently mix and disperse the above materials; then 0.4mL of acetic acid (12M) was added, the mixture was shaken well, and the reaction was carried out at room temperature for 72h; the resulting brown yellow solid was collected, washed with 25mL of methanol, centrifuged at 8000rpm/min for 10 minutes, washed and centrifuged three times, and dried under vacuum at room temperature overnight.
Example 3 Fe 3O4 Synthesis of COFs
Fe 3O4 (50 mg, synthesized according to the prior art), TAPB (0.04 mmol) and DHTP (0.06 mmol) were placed in a 50mL single-port bottle, and then 5mL acetonitrile was added thereto, and the above mixture was sonicated for 1min in order to sufficiently mix and disperse the above materials; then 0.4mL of acetic acid (12M) was added, the mixture was shaken well, and the reaction was carried out at room temperature for 72h; the resulting brown yellow solid was collected, washed with 25mL of methanol, centrifuged at 8000rpm/min for 10 minutes, washed and centrifuged three times, and dried under vacuum at room temperature overnight.
Experimental example
In the following experimental examples, the standard sample of the sulfonamide antibiotics is purchased from Sigma company, the sample is the sulfonamide antibiotics, and all the solutions are stored in a refrigerator at 4 ℃.
MALDI MS analysis experiments were carried out using model rapifleX TM from Bruce, the laser wavelength being 337nm, the voltage being between-20 and 20kV, and the negative ion mode being 1000shots.
Sample preparation
Alpha-cyano-4-hydroxycinnamic acid (HCCA) matrix was dissolved in water with 0.1% TFA: acetonitrile=15: 85. configuration;
2, 5-dihydroxybenzoic acid (DHB) matrix was dissolved in water with 0.1% TFA: acetonitrile=70: 30 configuration;
10mg of the core-shell Fe 3O4 @COFs prepared in example 1 is taken to be dispersed in water/methanol (1/1), ultrasonic treatment is carried out for 1 min, 1 mu L of target object is firstly dripped on a target plate, after natural airing, 1 mu L of core-shell Fe 3O4 @COFs is dripped on the target object, and after natural airing, the target object is to be detected.
1. Characterization of core-shell Fe 3O4 @ COFs material
The nanomaterial Fe 3O4 @ COFs prepared in example 1 and the magnetic material Fe 3O4 were selected for characterization.
In FIG. 1, a is a scanning electron microscope image of ferroferric oxide (Fe 3O4), and it can be seen that the magnetic sphere has about 200nm, and in addition, in the transmission electron microscope image of ferroferric oxide (Fe 3O4) (b in FIG. 1), the magnetic core has about 150-200nm, and the description is consistent with the characterization of the scanning electron microscope image. In FIG. 1, c is a scanning electron microscope image of Fe 3O4 @COFs, the spherical morphology of the material can be seen, the particle size of the material is larger than 200nm and about 250nm, and further, the transmission electron microscope of d in FIG. 1 is used for characterizing the compounded Fe 3O4 @COFs, so that the core-shell structure of the sample can be seen. The scheme of the invention successfully synthesizes the Fe 3O4 @COFs nano material with the expected core-shell structure as can be seen from a scanning electron microscope and a transmission electron microscope shown in the whole figures 1 a-d.
Based on the XPS data shown in FIG. 2a, it can be seen that the nanomaterial contains Fe2p, O1s, N1s, and C1s. Whereas the hysteresis curve shown in fig. 2 b gives 40.2emu/g of Fe 3O4 @ COFs. The infrared data shown in fig. 2C shows that Fe-O-Fe vibration has a typical absorption band at 586cm -1, and absorption at 3421, 1640 and 1388cm -1 indicates the presence of hydroxyl groups, and that the prepared Fe 3O4 @cofs exhibit new characteristic peaks at 1450-1600 and 1610cm -1, respectively, associated with the benzene skeleton and c=n vibration of COFs materials. The nitrogen adsorption-desorption curve shown in fig. 2 d represents that the specific surface area of Fe 3O4 @COFs is 173cm 3/g, a large specific surface area can provide more binding sites, more molecules are adsorbed, and the diameter of the pore size is 4.3nm, so that the catalyst is suitable for small-molecule sulfonamide compounds.
2. Comparison of Fe 3O4 @ COF as matrix Material with other materials
In fig. 3, a is a blank matrix mass spectrum of the nano material Fe 3O4 @COFs, and it can be seen that the Fe 3O4 @COFs has a clean background in the range of m/z 200-400 and no interference.
In fig. 3, b is the result of the response of Fe 3O4 @ COFs to the detection mass spectrum of 6 sulfonamide antibiotics using the matrix, it can be seen that Fe 3O4 @ COFs has a lower background interference peak, and a correspondingly stronger signal and higher sensitivity than the conventional matrices HCCA (c in fig. 3) and DHB (d in fig. 3); it can be seen that 6 sulfonamides were all detected in the base of Fe 3O4 @ COFs, whereas 4 were detected for HCCA and 5 were detected for DHB. Similarly, compared with the graphene shown in fig. 3e, the Fe 3O4 @COFs material synthesized by the method has stronger signal correspondence, more target objects are identified by comparison, and the signal correspondence is 3 times of that of the pure ferroferric oxide in fig. 3 f.
As can be seen from the data in table 1 below, the Relative Standard Deviation (RSD) for the point-to-point and sample-to-sample (n=15) was 5.78-9.32% and 6.54-10.2%, respectively. Thus, satisfactory reproducibility is due to the Fe 3O4 @ COFs having efficient laser energy transfer to the target analyte; it is also illustrated that Fe 3O4 @ COFs can uniformly deposit samples on the target plate to ensure reproducibility of analysis results, while the nanopore structure of hydroxyl polar groups can effectively prevent aggregation and accelerated desorption of analytes in MALDI.
Table 1 Fe 3O4 @ COFs reproducibility study on 6 sulfanilamide assays
| Analyte(s) | m/z | Point-to-point RSD (%) | Sample to sample RSD (%) |
| Sulfonacetamides (SA) | 213.14 | 5.78 | 6.54 |
| Sulfadiazine (SD) | 249.13 | 6.66 | 7.97 |
| Sulfathiazole (STZ) | 254.18 | 8.73 | 10.2 |
| Sulfoisoxazoles (SIX) | 266.08 | 6.83 | 8.88 |
| Sulfadimidine (SMZ) | 277.30 | 9.32 | 9.32 |
| Sulfadimidine (SDX) | 309.28 | 7.87 | 8.81 |
3. Salt tolerance and reproducibility investigation of Fe 3O4 @ COF as substrate
In this experimental example, salt tolerance was examined with 5ng/mL of sulfoacetamide, and the results are shown in FIG. 4. When the concentration of KCl is increased to 500mM, the signal intensity is reduced to 82.5%, and the signal intensity is kept basically unchanged when the concentration of KCl is increased, which shows that Fe 3O4 @COFs has good salt tolerance as a matrix in an anion mode.
4. Condition optimization of extracting sulfanilamide by using Fe 3O4 @ COF as adsorbent
The experimental example is based on the material consumption, pH intensity and extraction time, which are important parameters for adsorption experiments, and optimizing the philosophy parameters has important significance for obtaining the optimal experimental effect.
As can be seen from the results shown in FIG. 5, the signal intensity was optimal when the amount was 0.5 mg/mL; the pH is between 5 and 9 units to a better intensity, whereas the neutral 7 is essentially the best signal intensity; when the extraction time is 15min, the signal intensity is optimal, and the enrichment efficiency is best.
5. Method for evaluating sulfonamide by using Fe 3O4 @COF as adsorbent and matrix for assisting laser analysis ionization mass spectrometry
Under the optimal experimental conditions obtained in the experimental example 4, a method for analyzing small sulfonamide molecules by Fe 3O4 @COFs auxiliary laser analysis ionization mass spectrometry is further established, the linear equation of each sulfonamide molecule is shown in figure 6, the obtained parameters are shown in table 2, the linear range of 0.05-10ng/mL, the detection limit of 0.01-0.02ng/mL and the quantitative limit of 0.04-0.07ng/mL are obtained. The relative standard deviation of the repeated and repeated marking of the same sample at different positions of the same spot plate is 7.45-13.4%, and the relative standard deviation of the marking of the same sample at different spot plates is 6.88-12.7%, which shows that the method has better reproducibility.
Table 2 analytical performance parameters of the method
6. Determination of sulfonamide antibiotics in environmental water sample
To 2mL of a blank water sample, 100. Mu.L of Fe 3O4 @ COFs (0.5 mg/mL in water) was added to enrich the target analyte, incubated at room temperature for 45min, separated with a magnet, and the solid fraction was redispersed in 100. Mu.L of water. 1 μl was deposited on the MALDI target for analysis. And (3) performing standard adding experiments on the water samples at different concentrations, wherein the steps are the same as the sample preparation operation steps. The collected environmental water sample is filtered by a filter membrane with the diameter of 0.45 mu m, suspended matters are filtered, and the environmental water sample is refrigerated in a refrigerator.
The experiment was analyzed with model rapifleX TM from Bruce, the laser wavelength was 337nm, the voltage was between-20 and 20kV, and the negative ion mode was 1000shots.
As shown in the result of FIG. 7, the blank environmental water sample does not detect the characteristic peak of the target object, the signal peak of the sample can be detected after 0.1ng/mL of standard sample is added, the signal intensity of the sample can be detected after the Fe 3O4 @COFs is enriched, and the recovery rate of the sample is 78.9% -94.5%.
7. Other sample analysis
Milk sample
2ML of blank milk is taken, protein is precipitated by acetic acid buffer solution, the solution is centrifuged, supernatant is taken, and 100 mu L of Fe 3O4 @COFs (0.5 mg/mL in water) is added to the supernatant to enrich target analytes. Incubate at room temperature for 45min, separate with magnet, and re-disperse the solid fraction in 100 μl of water. 1 μl was deposited on the MALDI target for analysis. And (3) performing standard adding experiments on milk samples with different concentrations, wherein the steps are the same as the sample preparation operation steps.
The method for analyzing the sulfonamide micromolecules by using Fe 3O4 @COFs assisted laser desorption ionization mass spectrometry is used for analyzing milk samples, the linear range is 0.1-20ng/mL, the detection limit is 0.02-0.04ng/mL, and the quantitative limit is 0.07-0.15ng/mL. The relative standard deviation of the repeated and repeated dotting of the same sample at different positions of the same dotting plate is 6.62-13.1%, the relative standard deviation of the dotting of the same sample at different dotting plates is 7.22-13.2%, which shows that the method has better reproducibility, and the recovery rate of the sample is 81.3% -101.2%.
Meat sample
Taking 1g of meat sample (pork or fish), dispersing in 10mL of acetonitrile after homogenizing, oscillating to extract sulfonamide target substances, drying with nitrogen, re-dissolving in 2mL of ultrapure water, adding 100 mu L of Fe 3O4 @COFs (0.5 mg/mL in water) to enrich target analytes, incubating for 45min at room temperature, separating with a magnet, and re-dispersing solid parts in 100 mu L of water. 1 μl was deposited on the MALDI target for analysis. And (3) performing marking experiments on meat samples at different concentrations, wherein the steps are the same as the sample preparation operation steps.
The Fe 3O4 @COFs assisted laser desorption ionization mass spectrometry method for analyzing the sulfonamide micromolecules is used for analyzing pork samples, the linear range is 0.1-20ng/g, the detection limit is 0.02-0.04ng/g, and the quantitative limit is 0.07-0.15 ng/g. The relative standard deviation of the repeated and repeated dotting of the same sample at different positions of the same dotting plate is 5.54-11.8%, the relative standard deviation of the dotting of the same sample at different dotting plates is 7.01-12.5%, which shows that the method has better reproducibility and the recovery rate of the sample is 83.2% -97.5%.
The method for analyzing the small sulfonamide molecules by using the Fe 3O4 @COFs assisted laser desorption ionization mass spectrometry is used for analyzing fish samples, the linear range is 0.1-20ng/g, the detection limit is 0.02-0.04ng/g, and the quantitative limit is 0.07-0.15 ng/g. The relative standard deviation of the repeated and repeated dotting of the same sample at different positions of the same dotting plate is 8.87-12.4%, the relative standard deviation of the dotting of the same sample at different dotting plates is 6.44-14.5%, which shows that the method has better reproducibility and the recovery rate of the sample is 80.3% -96.3%.
In summary, the invention applies the core-shell Fe 3O4 @COFs as a novel matrix integrating enrichment function into matrix-assisted laser desorption ionization mass spectrometry for the first time to detect small sulfonamide molecules in environmental water samples and food organisms. The result shows that the composite nano material shows background interference, high sensitivity and better reproducibility, and the established method is further applied to detection of an actual sample, so that the result is satisfactory. The method lays a foundation for the development of the detection of Fe 3O4 @COFs in other small molecule fields.
The foregoing descriptions of specific exemplary embodiments of the present invention are presented for purposes of illustration and description. It is not intended to limit the invention to the precise form disclosed, and obviously many modifications and variations are possible in light of the above teaching. The exemplary embodiments were chosen and described in order to explain the specific principles of the invention and its practical application to thereby enable one skilled in the art to make and utilize the invention in various exemplary embodiments and with various modifications as are suited to the particular use contemplated. It is intended that the scope of the invention be defined by the claims and their equivalents.
Claims (5)
1. A method for rapidly analyzing and detecting sulfonamide antibiotics based on auxiliary matrix laser analysis ionization mass spectrometry technology is characterized in that,
The method comprises the step of detecting sulfonamide antibiotics in a sample to be detected by taking a magnetic hydroxyl nano material Fe 3O4 @COFs as a matrix; the preparation method of the magnetic hydroxyl nano material Fe 3O4 @COFs comprises the following steps: a step of synthesizing by taking monodisperse Fe 3O4 nano particles, 1,3, 5-tri (4-aminophenyl) benzene and 2,5, dihydroxyterephthalaldehyde as monomers and acetonitrile as a solvent system;
Wherein the temperature of the synthesis reaction is room temperature, and the reaction time is 48-120h.
2. The method for rapid analysis and detection of sulfonamide antibiotics according to claim 1, wherein the molar ratio of 1,3, 5-tris (4-aminophenyl) benzene to 2,5, dihydroxyterephthalaldehyde is 1:1-2.
3. The method for rapid analysis and detection of sulfonamide antibiotics according to claim 1 or 2, wherein the mass ratio of the monodisperse Fe 3O4 nanoparticles to 1,3, 5-tris (4-aminophenyl) benzene and 2,5, dihydroxyterephthalaldehyde is 50-100:15:10.
4. The method for rapid analysis and detection of sulfonamide antibiotics based on the auxiliary matrix laser desorption ionization mass spectrometry technology according to claim 1, wherein the preparation method of the magnetic hydroxyl nanomaterial Fe 3O4 @COFs further comprises the steps of collecting a reaction product, washing, centrifuging and drying.
5. The method for rapid analysis and detection of sulfonamide antibiotics according to claim 1, wherein the sample to be detected comprises an environmental water sample, a milk sample or a meat sample.
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