CN111157665B - Liquid phase-tandem mass spectrometry analysis method of sulfonamide antibiotics - Google Patents
Liquid phase-tandem mass spectrometry analysis method of sulfonamide antibiotics Download PDFInfo
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- 229940123317 Sulfonamide antibiotic Drugs 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title claims abstract description 25
- 239000007788 liquid Substances 0.000 title claims abstract description 11
- 238000010846 tandem mass spectrometry analysis Methods 0.000 title claims abstract description 6
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- 238000001514 detection method Methods 0.000 claims abstract description 19
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 42
- 238000002414 normal-phase solid-phase extraction Methods 0.000 claims description 38
- 239000000243 solution Substances 0.000 claims description 31
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- 239000012071 phase Substances 0.000 claims description 14
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- 229960004306 sulfadiazine Drugs 0.000 claims description 11
- 229960005404 sulfamethoxazole Drugs 0.000 claims description 9
- JLKIGFTWXXRPMT-UHFFFAOYSA-N sulphamethoxazole Chemical compound O1C(C)=CC(NS(=O)(=O)C=2C=CC(N)=CC=2)=N1 JLKIGFTWXXRPMT-UHFFFAOYSA-N 0.000 claims description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 8
- 238000010828 elution Methods 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
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- 239000007791 liquid phase Substances 0.000 claims description 6
- 238000004949 mass spectrometry Methods 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
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- ASWVTGNCAZCNNR-UHFFFAOYSA-N sulfamethazine Chemical compound CC1=CC(C)=NC(NS(=O)(=O)C=2C=CC(N)=CC=2)=N1 ASWVTGNCAZCNNR-UHFFFAOYSA-N 0.000 claims description 6
- 239000006228 supernatant Substances 0.000 claims description 6
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- JNMRHUJNCSQMMB-UHFFFAOYSA-N sulfathiazole Chemical compound C1=CC(N)=CC=C1S(=O)(=O)NC1=NC=CS1 JNMRHUJNCSQMMB-UHFFFAOYSA-N 0.000 claims description 4
- 229960001544 sulfathiazole Drugs 0.000 claims description 4
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- 239000012498 ultrapure water Substances 0.000 claims description 4
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- 238000001819 mass spectrum Methods 0.000 claims description 2
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- 238000004885 tandem mass spectrometry Methods 0.000 claims description 2
- 238000000889 atomisation Methods 0.000 claims 1
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- 238000011160 research Methods 0.000 abstract description 11
- 238000001294 liquid chromatography-tandem mass spectrometry Methods 0.000 abstract description 6
- 238000004458 analytical method Methods 0.000 abstract description 5
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- 239000007790 solid phase Substances 0.000 abstract 1
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- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- 230000000694 effects Effects 0.000 description 12
- 229940124530 sulfonamide Drugs 0.000 description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 11
- 150000003456 sulfonamides Chemical class 0.000 description 11
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- 241000282376 Panthera tigris Species 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
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- YSIIHTHHMPYKFP-UHFFFAOYSA-N 2,5-dimethoxyterephthalaldehyde Chemical compound COC1=CC(C=O)=C(OC)C=C1C=O YSIIHTHHMPYKFP-UHFFFAOYSA-N 0.000 description 1
- 208000031295 Animal disease Diseases 0.000 description 1
- 101000878457 Macrocallista nimbosa FMRFamide Proteins 0.000 description 1
- 241000202964 Mycoplasma mobile Species 0.000 description 1
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
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- 238000000634 powder X-ray diffraction Methods 0.000 description 1
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- 239000007858 starting material Substances 0.000 description 1
- FDDDEECHVMSUSB-UHFFFAOYSA-N sulfanilamide Chemical compound NC1=CC=C(S(N)(=O)=O)C=C1 FDDDEECHVMSUSB-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/88—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/08—Selective adsorption, e.g. chromatography
- B01D15/10—Selective adsorption, e.g. chromatography characterised by constructional or operational features
- B01D15/20—Selective adsorption, e.g. chromatography characterised by constructional or operational features relating to the conditioning of the sorbent material
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/88—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86
- G01N2030/8809—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86 analysis specially adapted for the sample
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Abstract
The invention belongs to the technical field of detection of sulfonamide antibiotics, and particularly relates to a liquid phase-tandem mass spectrometry analysis method of sulfonamide antibiotics. The invention provides a TPB-DMTP-COF material in the previous research, and provides the application of the material in the enrichment aspect of sulfonamide antibiotics aiming at further research on the organic framework material. In addition, the invention also establishes a new method for analyzing 6 sulfonamide antibiotics residues in water and food samples by solid phase extraction-liquid chromatography-tandem mass spectrometry on the basis. The method has the advantages of good repeatability, wide linear range, low detection limit and reliable result, meets the detection requirement, and can realize the rapid analysis of the sulfonamide antibiotics in the actual sample.
Description
Technical Field
The invention belongs to the technical field of detection of sulfonamide antibiotics, and particularly relates to application of a TPB-DMTP-COF material as a sulfonamide component solid-phase extraction material and a liquid-tandem mass spectrometry analysis method of the sulfonamide antibiotics.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
Sulfonamides antibiotics are chemically synthesized antibacterial substances and are widely applied to preventing animal diseases. In recent years, the residues of sulfonamide antibiotics enter soil and water through various ways, and cause great harm to the ecological environment and food safety. Therefore, it is very important to establish a rapid, sensitive and reliable analytical method for detecting sulfonamide residues in food and water samples.
Various techniques are currently used for the determination of sulfonamides, such as colloidal gold immunochromatography, capillary electrophoresis, high performance liquid chromatography, and liquid chromatography-tandem mass spectrometry, among others. Among these techniques, liquid chromatography-tandem mass spectrometry has become the most effective technique for analyzing sulfonamides.
Sample pretreatment is crucial to establish an analytical method for sulfonamide antibiotic residues in a complex matrix. At present, commonly used sample pretreatment methods for treating sulfonamide antibiotics in complex matrixes mainly comprise liquid-liquid extraction, pressurized liquid extraction, solid-phase extraction, matrix solid-phase dispersion methods and QuEChERs extraction methods. Among them, the solid phase extraction method has the advantages of simplicity, convenience, rapidness and the like, and is used for extracting sulfonamide antibiotics from food and environmental water samples. Adsorbents are the core part of solid phase extraction, mainly because they can achieve high-fold enrichment of targets in trace analysis. Materials such as C18, HLB, magnetic multi-walled carbon nanotubes and magnetic molecularly imprinted polymers have been successfully used as solid phase extraction adsorbents.
Covalent organic backbone materials (COFs) are a class of crystalline microporous polymers with a regular structure that can control the chemistry of the material surface by the precise introduction of molecular recognition groups or catalytic sites. The COF material has the characteristics of high thermochemical stability, large specific surface area, high porosity, low density, a permanent open pore structure and the like, and has a wide application prospect in the field of environment. The TPB-DMTP-COF material provided by the inventor in the previous research of research teams has good acid-base stability and can be applied to the detection of trace phenol in a water sample.
Disclosure of Invention
Aiming at the research background, the invention carries out extended research on the application of the COF material, and the research shows that the COF material is stable in solutions with different pH values and organic solutions, has good adsorption effect on sulfonamide components, has good enrichment effect on trace sulfonamide antibiotic residues in a sample to be detected, can be applied to the detection of sulfonamide antibiotics, and is beneficial to improving the sensitivity and accuracy of detection.
The first aspect of the invention provides a solid phase extraction material, wherein the solid phase extraction material is a TPB-DMTP-COF material, and the TPB-DMTP-COF material has a uniform spherical structure and is 1500-1600 cm in length -1 And 1600-1680 cm -1 Has an absorption peak in the range, and the specific surface area is 1400-1500 m 2 g -1 The pore diameter is 2-3 nm.
Preferably, the TPB-DMTP-COF material is obtained by reacting TABP and DMTA through Schiff base.
Further preferably, the preparation method of the TPB-DMTP-COF material comprises the following steps: TAPB, DMTA, 1, 4-dioxane, 1,3, 5-trimethylbenzene and glacial acetic acid are fully mixed in a round-bottom flask and react for 68-75 h at room temperature to obtain light yellow precipitate.
In a second aspect of the invention, there is provided the use of the solid phase extraction material of the first aspect in the detection of sulfonamide moieties.
Preferably, the sulfonamide component is sulfonamide antibiotics; further, it comprises Sulfadiazine (SD), Sulfathiazole (SP), Sulfapyridine (ST), sulfadiazine (SM1), sulfadimethy pyrimidine (SM2) and Sulfamethoxazole (SMX).
In a third aspect of the present invention, a method for liquid phase-tandem mass spectrometry analysis of sulfonamide antibiotics is provided, wherein the detection method comprises enriching a sample to be detected by using the solid phase extraction material of the first aspect.
Preferably, the detection method comprises the following steps: pretreating a sample to be detected to obtain an extracting solution; the extracting solution is enriched by the solid phase extraction material of the first aspect, the enriched sample is eluted to obtain a solution to be detected, and the solution to be detected is detected by liquid phase-mass spectrometry.
Further preferably, the pretreatment step is as follows:
adding an acetonitrile aqueous solution into a sample to be detected, extracting, centrifuging to obtain a supernatant part, adding a saturated n-hexane solution of acetonitrile into the supernatant part, separating to obtain an acetonitrile part, drying with nitrogen, and re-dissolving with ultrapure water to obtain an extracting solution.
In some specific embodiments, the volume ratio of acetonitrile to water in the acetonitrile water solution is 100: 2-5.
In some embodiments, the step of extracting comprises vortexing and water bath shaking.
Further preferably, the specific steps of enriching the sample to be tested are as follows: fixing the solid phase extraction material in the first aspect in a solid phase extraction column, connecting one end of the solid phase extraction column with a vacuum pump, sucking a sample to be detected into the solid phase extraction column through a sampler at the other end, and adding an organic reagent for elution to obtain a liquid to be detected.
In some specific embodiments, the eluent is methanol.
Further preferably, the liquid phase detection is performed by using a C18 chromatographic column.
Further preferably, the liquid phase mobile phase: the organic phase was acetonitrile and the aqueous phase was 0.1% formic acid.
Further preferably, the liquid phase adopts a gradient elution mode, and specifically, the gradient elution procedure is as follows: and (3) 0-4 min, reducing the C phase from 90% to 60%, 4-4.01 min, increasing the C phase from 60% to 90%, 4.01-5.5 min, and keeping the C phase unchanged at 90%.
Further preferably, the flow rate of the liquid phase is 0.3-0.5 mL/min.
Further preferably, the mass spectrometry conditions are as follows: the voltage of the ion spray is-4500V; source temperature: 500 ℃; curtain gas: 40 psi; or inlet voltage (EP): -10V; collision cell exit voltage: -13V; atomizer gas and turbine gas pressure: 50 psi.
Further preferably, the mass spectrometry ion source gas 1(GS1) and the ion source gas 2(GS2) are both 50 psi; or both the collision gas and the atomizing gas are nitrogen.
In some specific embodiments, the Sulfadiazine (SD), Sulfathiazole (SP), Sulfapyridine (ST), sulfadiazine (SM1), sulfadimetrazine (SM2), and Sulfamethoxazole (SMX) MRM conditions are set forth in table 1 below:
TABLE 1 LC-MS/MS MRM data acquisition method for sulfonamide antibiotics
Compared with the prior art, the invention has the beneficial effects that:
1. in the previous research of the research team of the inventor, the TPB-DMTP-COF material and the good adsorption effect of the material on phenol are provided. The invention expands the application of the COF material, provides good adsorption effect of the COF material on sulfonamide antibiotics, and provides a research basis for the application of the COF material in the field of solid phase extraction.
2. The invention researches the enrichment condition of the COF material applied to sulfonamide antibiotics and provides a detection method of liquid phase-mass spectrum tandem connection. The detection limit of the detection method provided by the invention to 6 sulfanilamide components is 0.5-1.0 ng L -1 And the detection is sensitive.
3. The TPB-DMTP-COF material has good stability, the invention also provides an elution condition suitable for the solid phase extraction material, good elution effect can be realized by adopting methanol eluent with pH of 6, the prepared extraction column can be repeatedly used for many times without influencing the recovery effect, and the economic cost can be obviously reduced when the TPB-DMTP-COF material is applied to actual detection.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the invention and together with the description serve to explain the invention and not to limit the invention.
FIG. 1 is a diagram showing the characterization of TPB-DMTP-COF in example 1;
wherein FIG. 1(A) is a scanning electron microscope image of × 10,000;
FIG. 1(B) is an infrared spectrum of the starting material and the product;
FIG. 1(C) is an XRD pattern;
FIG. 1(D) is a nitrogen adsorption curve and a pore size distribution diagram.
FIG. 2 is a Fourier infrared spectrum of TPB-DMTP-COF in example 1 in various media;
wherein, fig. 2(a) is in air;
fig. 2(b) is soaking in a solution with pH 2 for 24 h;
fig. 2(c) is soaking in solution with pH 7 for 24 h;
fig. 2(d) is soaking in solution with pH 12 for 24 h;
FIG. 2(e) shows methanol soaking for 24 h;
FIG. 2(f) shows acetone soaking for 24 h;
figure 2(g) shows acetonitrile soaking for 24h,
FIG. 2(h) shows dichloromethane soaking for 24 h;
FIG. 2(i) shows n-hexane soaking for 24 h.
FIG. 3 is a graph showing the effect of different experimental conditions on extraction recovery in example 1;
wherein, fig. 3(a) shows the eluent type;
FIG. 3(B) shows the eluent volume;
FIG. 3(C) shows the sample volume;
FIG. 3(D) shows pH.
FIG. 4 is a typical chromatogram of an actual sample in example 1;
wherein, FIG. 4(a) is a milk sample;
FIG. 4(b) shows milk with a label of 10 ng.L -1 ；
FIG. 4(c) shows milk labeled 50 ng.L -1 ；
FIG. 4(d) shows milk labeled with 100 ng.L -1 ；
In FIG. 4(d), peak No. 1 is SD; peak No. 2 is ST; the No. 3 peak is SP; peak No. 4 is SM 1; peak No. 5 is SM 2; peak No. 6 is SMX.
Detailed Description
It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the invention. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
As introduced in the background art, aiming at the defects in the prior art, the invention provides application of TPB-DMTP-COF as a solid phase extraction material in detection of sulfonamides antibiotics.
In order to make the technical scheme of the present invention more clearly understood by those skilled in the art, the technical scheme of the present invention will be described in detail below by combining specific examples and comparative examples.
Example 1
1 experimental part
1.1 instruments and reagents
The main instruments used in the experiment were: high performance liquid chromatography-triple quadrupole mass spectrometer. Methanol, acetonitrile, acetone, dichloromethane, n-hexane (chromatographically pure). 2, 5-dimethoxybenzene-1, 4-Dicarbaldehyde (DMTA), 1,3, 5-tris (4-aminophenyl) benzene (TAPB), 1, 4-dioxane and glacial acetic acid. Sulfadiazine (SD), Sulfathiazole (SP), Sulfapyridine (ST), and Sulfamethazine (SM) 1 ) Sulfadimidine (SM) 2 ) And Sulfamethoxazole (SMX). All reagents were stored at 4 ℃.
1.2 Synthesis of TPB-DMTP-COF
TAPB (0.64mmol, 224mg), DMTA (0.96mmol, 192mg), 1, 4-dioxane (6.0mL), 1,3, 5-trimethylbenzene (6.0mL) and glacial acetic acid (3.0M, 2.0mL) were mixed well in a 50mL round bottom flask and reacted at room temperature for 72h to give a pale yellow precipitate. The precipitate was separated by centrifugation and washed several times with methanol to remove impurities. Drying the obtained product in a vacuum drying oven at 80 ℃ for 12h to obtain TPB-DMTP-COF.
1.3 HPLC-MS/MS conditions
1.3.1 HPLC conditions
C18 column: 2.1 mm. times.100 mm, 2.6. mu.m. Mobile phase: phase C was 0.1% formic acid and phase D was acetonitrile. Gradient elution procedure: and (3) reducing the C phase from 90% to 60% in 0-4 min, and increasing the C phase from 60% to 90% in 4.01-5.5 min, wherein the C phase is kept unchanged at 90%. Equilibrate for 5min post column. Flow rate: 0.4 mL/min. Column temperature: 30 ℃, sample introduction: 5 μ L.
1.3.2 MS/MS conditions
Ion spray voltage: -4500V; source temperature: 500 ℃; curtain gas: 40 psi; inlet voltage (EP): -10V; collision cell exit voltage: -13V; atomizer gas and turbine gas pressure: 50 psi; ion source gas 1(GS1) and ion source gas 2(GS2) were both 50 psi. Both the collision gas and the atomizing gas are nitrogen. The optimal MRM conditions for the analytes are listed in table 1.
TABLE 1 LC-MS/MS MRM data acquisition method for sulfonamide antibiotics
1.4 preparation by solid phase extraction
50mg of TPB-DMTP-COF was placed in a solid phase extraction column (3mL) with a sieve plate, and then the material was immobilized in the solid phase extraction column with another sieve plate. And placing the assembled solid phase extraction column on a solid phase extraction device. One end of the solid phase extraction device is connected with the vacuum pump, and the other end of the solid phase extraction device is connected with the sample through the sampler. The solid phase extraction column was activated with methanol and washed with ultrapure water before use.
1.5 sample Collection and processing
Pond water, black tiger spring water, milk and pork are collected as actual samples. The milk and pork are treated according to the national standard GB/T21316-2007: 2 grams of homogenized pork or milk was added to a 50mL disposable centrifuge tube and 25mL of an aqueous acetonitrile solution (acetonitrile to water volume ratio 100: 3) was added. The mixture was vortexed with a vortexer for 1 minute to mix well, and further shaken with a water bath shaker for 30 minutes to extract the sulfonamide antibiotics in the sample. The supernatant was separated by centrifugation (8000rpm, 5 minutes, 9 Xg rcf) in a centrifuge. 25ml of acetonitrile-saturated n-hexane solution were added to the extract and shaken for 5 minutes. After separation, the supernatant was discarded, and the bottom acetonitrile solution was collected. The solution was then blown dry with a stream of nitrogen and reconstituted to 100mL with ultra pure water. The pond water, the black tiger spring water and the processed milk and pork samples are filtered by a microporous filter membrane of 0.45 mu m and then stored in a brown glass bottle at the temperature of 4 ℃ for later use.
2 results and discussion
2.1 characterization of TPB-DMTP-COF
The scanning electron microscope of TPB-DMTP-COF is shown in FIG. 1A, and the TPB-DMTP-COF has a uniform spherical structure (1-2 μm). Infrared ray is shown in FIG. 1B, because the characteristic peak C ═ O (1,678 cm) -1 ) And N-H (3435, 3354 and 3209 cm) -1 ) While disappearing at 1591cm -1 And 1614cm -1 Two absorption peaks were found, which correspond to C ═ C and C ═ N bonds, respectively. The results show that Schiff base reaction has occurred between TABP and DMTA monomers, and TPB-DMTP-COF has been successfully synthesized. X-ray powder diffraction as shown in fig. 1C, the appearance of six diffraction peaks (2 θ ═ 2.77,4.82,5.56,7.34,9.65, and 25.28 °) indicates that TPB-DMTP-COF has a very good crystal structure. The specific surface area of TPB-DMTP-COF is as high as 1431m 2 g -1 (FIG. 1D), surpassing many conventional solvothermal synthesized covalent organic framework materials. The high specific surface area provides more adsorption sites for extracting the sulfonamide antibiotics, thereby enhancing the enrichment capacity. FIG. 1D (inner panel) shows that the pore diameter of TPB-DMTP-COF is 2.32nm, and the large pore diameter is beneficial to the micromolecule sulfonamide antibiotics to enter the interior of the COF more easily, so that the extraction capacity is improved.
The chemical stability of TPB-DMTP-COF material in different pH value solutions and organic solvents (methanol, acetone, acetonitrile, dichloromethane and n-hexane) is examined. As can be seen from FIG. 2, the Fourier infrared spectrograms of TPB-DMTP-COF materials in different pH values of solutions and organic solvents have no obvious change compared with that in air, which shows that TPB-DMTP-COF is stable in different pH values of solutions and organic solvents, so that TPB-DMTP-COF has the potential of being used as a solid phase extraction adsorbent.
2.2 optimization of the Experimental conditions
TPB-DMTP-COF was used as a solid phase extraction sorbent in combination with LC-MS/MS for the determination of trace sulfonamide antibiotics (SD, ST, SP, SM1, SM2 and SMX) in water. The extraction conditions (sample volume and pH) and desorption conditions (type and volume of eluent) were optimized for optimal experimental parameters. Optimizing each sulphur in the water sample used in the experimentThe concentration of the amine antibiotics is 200ng L -1 . As shown in figure 3, the extraction effect of TPB-DMTP-COF material on sulfonamide antibiotics is evaluated by adopting the recovery rate of 6 sulfonamide antibiotics.
In the solid phase extraction process, the type of eluent is an important factor influencing the extraction effect. In this experiment, five solvents (methanol, acetone, acetonitrile, dichloromethane and n-hexane) were selected as eluents, as shown in fig. 3A. As can be seen from the figure, methanol has the highest extraction efficiency. Therefore, methanol was chosen as eluent for this experiment.
The volume of the eluent is also one of the main factors influencing the desorption effect of the sulfonamide antibiotics. Figure 3B shows that as the volume of methanol in the eluent increases, the recovery gradually increases, reaching a certain amount and remaining constant. Finally, the volume of methanol was determined to be 10 ml.
The amount of sample may be another factor affecting the effectiveness of the experiment. In this work, the effect of five different sample volumes (50ml, 100ml, 200ml, 400ml, 600ml) on the recovery of six sulfonamide antibiotic targets was studied. As can be seen from FIG. 3C, the recovery of sulfonamide antibiotics varied slightly over the sample size range of 50-600 mL. In order to save extraction time and ensure extraction effect, the sample amount was determined to be 100 mL.
The influence of the pH value of the solution on the recovery rate of the solid-phase extraction sulfonamide antibiotics is investigated. The pH value range of the solution selected in the experiment is 2-10, and the result is shown in figure 3D. As can be seen from fig. 3D, the recovery of the six sulfonamides was highest at pH 6. For best experimental results, in the following experiments, the pH was chosen to be 6.
In conclusion, the best experimental conditions of TPB-DMTP-COF on the solid-phase extraction of six sulfonamides are as follows: methanol was used as the eluent, the volume of the eluent was 10mL, the volume of the sample was 100mL, and the pH of the solution was 6.
2.3 methodological parameters
Under the optimized condition, the linear range of the method is 5-1000 ng L -1 Coefficient of correlation R 2 0.991 to 0.997. The detection limit of 6 sulfonamides antibiotics is 0.5-1.0 ng L calculated by the signal-to-noise ratio S/N ═ 3 -1 To (c) to (d); the method has the quantitative limit of 1.6-3.5 ng L by taking the S/N ratio as 10 -1 Within the range of (1). Relative standard deviations between day-to-day (n-3) and day-to-day (n-3) were 4.6-8.7% and 2.5-7.0%, respectively, for the six sulfonamides. The relative standard deviation among five identical TPB-DMTP-COF solid phase extraction columns is 3.8-7.3%. Each TPB-DMTP-COF extraction column can be reused for more than 20 times without obvious reduction of the recovery rate.
TABLE 2 analytical data for the solid phase extraction method
2.4 actual sample analysis
To evaluate the applicability of the above method, spring water, pond water, milk, and pork were selected as actual water samples to be analyzed. In the above four practical samples, no sulfonamide antibiotics were found. Four samples were added at 10, 50 and 100ng L -1 The three concentrations of the compound can obtain satisfactory standard addition recovery rate of 72.3-113.0%. Fig. 4 shows a typical chromatogram of a milk sample. The experimental results show that the method is feasible to be applied to the analysis of the sulfonamide antibiotic residues in the actual water samples and the food samples.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (3)
1. A method for liquid phase-tandem mass spectrometry analysis of sulfonamide antibiotics, comprising the steps of: pretreating a sample to be detected to obtain an extracting solution; enriching an extracting solution by adopting a solid-phase extraction material, eluting the enriched sample to obtain a solution to be detected, and detecting the solution to be detected by liquid-mass spectrometry;
the specific steps of enriching the extracting solution and eluting the enriched sample are as follows: fixing a solid-phase extraction material in a solid-phase extraction column, connecting one end of the solid-phase extraction column with a vacuum pump, sucking a sample to be detected into the solid-phase extraction column through a sampler at the other end, and adding an organic reagent for elution to obtain a liquid to be detected; the eluent is methanol, the volume of the eluent is 10mL, the volume of the sample is 100mL, and the pH of the solution is = 6;
the liquid phase detection adopts a C18 chromatographic column; liquid phase mobile phase: the organic phase is acetonitrile, and the aqueous phase is 0.1% formic acid; the gradient elution mode is adopted, and the gradient elution program is as follows: reducing the water phase from 90% to 60% in 0-4 min, and increasing the water phase from 60% to 90% in 4-4.01 min, and keeping the water phase unchanged at 90% in 4.01-5.5 min; the flow rate is 0.3-0.5 mL/min;
the mass spectrometry conditions were as follows: the voltage of the ion spray is-4500V; source temperature: 500 ℃; curtain gas: 40 psi; entrance voltage EP: -10V; collision cell exit voltage: -13V; atomizer gas and turbine gas pressure: 50 psi; the mass spectrum ion source gas 1 and the ion source gas 2 are both 50 psi; the collision gas and the atomization gas are both nitrogen;
the solid phase extraction material is a TPB-DMTP-COF material, and the TPB-DMTP-COF material has a uniform spherical structure and is 1500-1600 cm -1 And 1600-1680 cm -1 Has an absorption peak in the range, and the specific surface area is 1400-1500 m 2 g -1 The aperture is 2-3 nm; the TPB-DMTP-COF material is obtained by reacting TABP and DMTA through Schiff base; the preparation method of the TPB-DMTP-COF material comprises the following steps: TAPB, DMTA, 1, 4-dioxane, 1,3, 5-trimethylbenzene and glacial acetic acid are fully mixed in a round-bottom flask and react for 68-75 h at room temperature to obtain light yellow precipitate;
the sulfonamide antibiotics comprise sulfadiazine, sulfathiazole, sulfapyridine, sulfamethazine, sulfadimetrazine and sulfamethoxazole.
2. A method for the mass spectrometry of sulfa antibiotics according to claim 1, characterized in that said pretreatment step is as follows:
adding an acetonitrile water solution into a sample to be detected, extracting, centrifuging to obtain a supernatant part, adding a saturated n-hexane solution of acetonitrile into the supernatant part, separating to obtain an acetonitrile part, drying with nitrogen, and re-dissolving with ultrapure water to obtain an extracting solution.
3. The method for liquid phase-tandem mass spectrometry of the sulfonamide antibiotics of claim 2, wherein the volume ratio of acetonitrile to water in the acetonitrile aqueous solution is 100: 2-5; or the extraction step comprises vortex and water bath oscillation extraction.
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