CN113588822A - Solid phase micro-extraction head and preparation method and application thereof - Google Patents
Solid phase micro-extraction head and preparation method and application thereof Download PDFInfo
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- 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
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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
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
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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
- G01N30/86—Signal analysis
- G01N30/8675—Evaluation, i.e. decoding of the signal into analytical information
- G01N30/8679—Target compound analysis, i.e. whereby a limited number of peaks is analysed
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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
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
- G01N2030/062—Preparation extracting sample from raw 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
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
- G01N2030/067—Preparation by reaction, e.g. derivatising the sample
Abstract
The invention provides a solid phase micro-extraction head, a preparation method and application thereof, belonging to the technical field of detection. The invention provides a novel solid-phase microextraction concept, develops a toothpick solid-phase microextraction head based on the concept, is an improvement and optimization of a pretreatment technology in a detection process of residual quantity of nitrofuran metabolites in animal-derived food, and has the characteristics of no need of a solvent, high extraction speed, good reproducibility, small sample consumption, simplicity and convenience in operation, capability of performing field analysis and the like. The solid phase micro-extraction head provided by the invention has high-efficiency adsorption and desorption capacity on the nitrofuran metabolites and excellent impurity removal capacity, can effectively improve the quantitative limit of the nitrofuran metabolites, and has an effect obviously superior to the national standard detection result.
Description
Technical Field
The invention belongs to the technical field of detection, and particularly relates to a solid-phase micro-extraction head, and a preparation method and application thereof.
Background
At present, the detection standards of nitrofuran drug metabolites mainly include high performance liquid chromatography-tandem mass spectrometry for detecting residual amounts of nitrofuran drug metabolites in GB/T21311-2007 animal-derived foods, and liquid chromatography-tandem mass spectrometry for determining residual amounts of nitrofuran drug metabolites in GB/T20752-2006 pork, beef, chicken, pork liver and aquatic products, and the methods in the standards are all high performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS), and liquid-liquid extraction and solid-phase extraction are commonly used for extraction and purification.
However, the above method has a wide range of liquid-liquid extraction extracts, and more substances are extracted, which may interfere with extremely complex samples; and the liquid-liquid extraction is completed manually, and automation cannot be realized. In addition, if the solid phase extraction method for measuring the residual quantity of nitrofuran metabolites in GB/T20752-2006 pork, beef, chicken, pork liver and aquatic products is adopted for pretreatment, the following defects are also existed: firstly, the column passing needs to be pre-washed by methanol and water → the extracting solution passes through the column → water is used for washing impurities → elution and other steps, and the operation is more complex; secondly, the cost of the solid phase extraction column is higher; the automation can be realized through a full-automatic solid phase extraction instrument, but the price of the full-automatic solid phase extraction instrument is high and expensive, and the full-automatic solid phase extraction instrument is difficult to be equipped in a common laboratory; fourthly, the problems of easy blockage, difficult elution and the like exist for the viscous and colloidal complex samples.
Disclosure of Invention
The solid phase micro-extraction head has high-efficiency adsorption and desorption capacity on the nitrofuran metabolites and excellent impurity removal capacity, can effectively improve the quantitative limit of the nitrofuran metabolites, and has an effect obviously superior to the national standard detection result.
In order to achieve the above object, the present invention provides a method for preparing a solid phase microextraction head, comprising the following steps:
dissolving polyacrylonitrile PAN powder in dimethylformamide, and stirring and dissolving at room temperature to obtain a saturated solution;
grinding the HLB particles to a preset particle size, adding the HLB particles into the PAN solution, and uniformly mixing to obtain PAN-HLB slurry;
fully shaking the obtained slurry at the rotating speed of 1800-;
fully shaking and cleaning the toothpick coated with the PAN-HLB slurry in a solvent solution at the rotating speed of 1500-1800 rpm to remove residues;
soaking the solid-phase micro-extraction head of the toothpick in a solvent with the volume ratio of 1: 1, activating HLB on the toothpick, and drying to obtain the solid phase micro-extraction head.
The technical scheme of the invention provides a novel solid-phase microextraction concept, and a toothpick solid-phase microextraction head is developed based on the concept, and the technology has the characteristics of no need of solvent, high extraction speed, good reproducibility, small sample consumption, simplicity and convenience in operation, capability of performing field analysis and the like, and is an improvement and optimization of a pretreatment technology in a detection process of residual quantity of nitrofuran metabolites in animal-derived food. It should be noted that the HLB particles used in the above scheme are commercially available, for example, from Waters corporation, which is a trade name of a solid phase extraction adsorbent, and a macroporous copolymer prepared by polymerizing two monomers, lipophilic divinylbenzene and hydrophilic N-vinyl pyrrolidone in a certain ratio has hydrophilic-lipophilic balance.
In particular, the Solid Phase Micro Extraction (SPME) technique employed in the present invention is significantly different from the existing Solid Phase Extraction (SPE) technique. The SPE technique has three important processes: firstly, a sample passes through a solid adsorbent, and target analytes in the sample are completely extracted; secondly, eluting the interference component from the adsorbent by using a leaching solvent; finally, the target analyte is eluted from the adsorbent using an elution solvent. The SPE pursues absolute recovery of the target, and thus each step of the SPE has strict operation requirements. However, commercial SPE filling processes use excessive amounts of filler, and the content of most positive samples remaining for detection is ppb, which causes great waste.
The difference is that the SPME technology adopted by the invention transfers target analytes from a sample system to the coating by utilizing the principles of equilibrium extraction and selective adsorption, and the SPME technology mainly comprises two steps: exposing the coating to the sample in a first step, the analyte being selectively extracted due to the extremely strong affinity of the coating for the analyte; in a second step, the substances extracted from the coating are desorbed. Since SPME does not need to completely adsorb the target, it pursues a relative recovery rate (achieved by internal standard method), which greatly simplifies the operation steps, reduces the detection cost, and greatly shortens the detection time.
Preferably, the particle size of the HLB particle is 25 to 30 μm. In one preference, the HLB particle size is 30 μm. It is understood that the particle size of the HLB particle is chosen because the particle size significantly affects the adsorption capacity of the test compound, and the adsorption factor increases with increasing particle size (350-500).
Preferably, the content of the HLB particles in the PAN-HLB slurry is 0.025g to 0.075 g. It is understood that the content of HLB particles in the above slurry is defined with the aim of PAN as an adsorbent for HLB and toothpick, and its content ratio with HLB significantly affects the preparation of SPME. If the mass of PAN is too large, the adsorption effect on the target molecule is affected by insufficient HLB ratio, while if the mass of PAN is too large, the adhesion to the toothpick is difficult, and therefore, the inventors have obtained the optimum ratio through many experiments.
Preferably, the solvent solution is a mixed solution of methanol, isopropanol and acetonitrile, and the volume ratio of the mixed solution is 50:25: 25.
The invention also provides the solid-phase micro-extraction head prepared by the preparation method according to any one technical scheme.
The invention also provides an application of the solid phase micro-extraction head in the technical scheme in the rapid detection of the residual quantity of nitrofuran metabolites in animal derived food.
The invention also provides a method for rapidly detecting the residual quantity of nitrofuran metabolites in animal derived food by using the solid phase microextraction head according to the technical scheme, which comprises the following steps:
placing the prepared solid phase micro-extraction head into the nitrofuran metabolite derivative liquid containing the animal-derived food with the well-adjusted pH, placing the liquid in a constant temperature oscillator at 36-37 ℃, and performing oscillation extraction for 30-40min at the rotating speed of 1500-;
taking out the solid phase micro-extraction head, putting the solid phase micro-extraction head into a centrifuge tube filled with water, and placing the solid phase micro-extraction head into a constant temperature oscillator at 36-37 ℃ to shake and clean at the rotating speed of 1500-;
after the cleaning, taking out the solid phase micro-extraction head, putting the solid phase micro-extraction head into a centrifuge tube filled with ethyl acetate, and placing the solid phase micro-extraction head into a constant temperature oscillator at 36-37 ℃ to perform oscillation desorption for 30-40min at the rotating speed of 1500-;
and then blowing the mixture to be dry by nitrogen at the temperature of 45-50 ℃, metering the volume to 0.5mL by using a mobile phase, filtering the mixture into a sample bottle by using a 0.2-micrometer filter membrane, and measuring the residual quantity of the nitrofuran metabolites by adopting liquid chromatography-mass spectrometry.
Preferably, the chromatographic conditions for the liquid chromatography mass spectrometry are as follows:
a chromatographic column: ZORBAXeclipsePlusC18(1.8 μm, 2.1 x 50 mm); column temperature: 40 ℃, flow rate: 0.3ml/min, sample size: 10 mu L of the solution; mobile phase: a: 10mM ammonium acetate + 0.1% formic acid water, B: methanol;
gradient elution procedure: 0 → 3.0min, from 10% B → 90% B; 3.0 → 5.0min, 90% B; 5.0 → 6.5min, equilibrium from 90% B → 10% B, 1 min.
Preferably, the mass spectrometric conditions for the liquid chromatography mass spectrometry are:
an ionization mode: ESI+(ii) a The scanning mode is as follows: multiple Reaction Monitoring (MRM); electrospray voltage: 5500V; atomization gas pressure (GS 1): 55 psi; air curtain pressure (CUR): 35 psi; assist gas pressure (GS 2): 50 psi.
Preferably, the preparation method of the nitrofuran metabolite derivative liquid containing the animal-derived food comprises the following steps:
adding a homogeneous sample containing animal-derived food into a 50mL polypropylene centrifuge tube, adding 30 μ L of 0.1 μ g/mL internal standard working solution, then respectively adding 17mL of 0.125mol/L hydrochloric acid solution and 1.0mL of derivative, homogenizing for 1min, and placing in a constant-temperature oscillator at 36-37 ℃ for keeping for 16-17 h;
centrifuging at 10000r/min for 10min, taking 10mL of supernatant, adding 1mL of dipotassium phosphate solution, and adjusting the pH to 7.0 by using 1mol/L sodium hydroxide solution and 0.1mol/L hydrochloric acid aqueous solution;
then adding 5mL of normal hexane, vortex mixing for 2min to remove oil, centrifuging for 10min at 10000r/min, and discarding the normal hexane layer to obtain the nitrofuran metabolite derivative liquid containing animal-derived food.
Compared with the prior art, the invention has the advantages and positive effects that:
1. the invention can realize the rapid detection of the residual quantity of the nitrofuran metabolites in the animal derived food by adopting the self-made solid-phase micro-extraction head, and the solid-phase micro-extraction head is prepared by wrapping about 1cm of filler on the toothpick head in the process, so that the traditional solid-phase extraction column is replaced, the cost is greatly saved on the premise of good effect, and one tenth of the cost of the solid-phase extraction column can be saved;
2. furthermore, in the detection process, a mode of oscillation stirring is adopted to replace column passing, so that the problems of easy blockage and difficult elution of viscous and colloidal complex samples are solved; meanwhile, the problems that the complex sample matrix liquid-liquid extraction purification effect is poor and interference possibly exists in the AHD detection process are solved (see figure 9);
3. furthermore, the method provided by the invention does not need to purchase an expensive full-automatic solid phase extraction instrument, and semi-automatic treatment of large-scale adsorption, cleaning and desorption of the toothpick solid phase micro-extraction head can be realized by means of constant-temperature oscillating water bath used in derivatization, so that the treatment efficiency is greatly improved.
Drawings
FIG. 1 is a chromatogram of 0.5. mu.g/kg chicken addition recovery AMOZ determined by the method in GB/T21311-2007;
FIG. 2 is a chromatogram of 0.5 μ g/kg chicken supplemented and recovered AMOZ provided in the example of the present invention;
FIG. 3 is a chromatogram of 0.5. mu.g/kg of added chicken recovery AOZ determined by the method in GB/T21311-2007;
FIG. 4 is a chromatogram of 0.5 μ g/kg chicken addition recovery AOZ provided by an embodiment of the present invention;
FIG. 5 is a chromatogram of 0.5 μ g/kg chicken addition recovery AHD determined by the method of GB/T21311-2007;
FIG. 6 is a chromatogram of 0.5 μ g/kg chicken supplemented with recycled AHD provided by the example of the present invention;
FIG. 7 is an SEM chromatogram of 0.5 μ g/kg chicken addition recovery determined by the method in GB/T21311-2007;
FIG. 8 is an SEM chromatogram of 0.5 μ g/kg chicken addition recovery provided by an embodiment of the invention;
fig. 9 shows the recycling situation of the toothpick solid phase extraction head developed by the invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The names and abbreviations of the four nitrofuran metabolites to which the present invention relates are shown in table 1:
TABLE 1 names and abbreviations for four nitrofuran metabolites
Example 1 preparation of solid phase micro-extraction head of toothpick
1. 7g polyacrylonitrile PAN powder was dissolved in 100mL Dimethylformamide (DMF) and stirred constantly at room temperature to ensure uniform dissolution.
2. Oasis HLB particles (30 μm) were milled for 2 hours at 240rpm using a ball mill.
3. 1g HLB was mixed with 10mL PAN solution to obtain the final PAN-HLB slurry. Then mixed on a shaker at 1800 rpm for 12 hours to provide a sufficiently homogeneous particle mixture.
4. Dipping PAN-HLB slurry with a toothpick, wherein the length of the slurry is about 1cm, uniformly coating the slurry on the toothpick, slightly drying the slurry, dipping the slurry once again,
5. the toothpick was rinsed twice with shaking (methanol, isopropanol and acetonitrile (MeOH/IPA/ACN, 50:25:25) in solvent solution at 1500 rpm for 15 minutes to remove residue.
6. Soaking the solid-phase micro-extraction head of the toothpick in a methanol/water mixturePretreatment in composition (MeOH/H2O, 50:50), activating HLB on the toothpick, and airing for later use.
Example 2 study of adsorption Effect of solid phase micro-extraction head of toothpick
1. Deriving a nitrofuran metabolite standard with a certain concentration, specifically:
200 mu L of 4 kinds of nitrofuran metabolite working solution with the concentration of 0.1 mu g/mL are taken, 17mL of 0.125mol/L hydrochloric acid solution and 1.0mL of 2-nitrobenzaldehyde are respectively added, the mixture is placed in a constant temperature oscillator for derivatization reaction at 37 ℃ for 16h, 1mL of dipotassium hydrogen phosphate solution is added, and the pH value is adjusted to be between 7.2 and 7.4 by 1mol/L sodium hydroxide solution and 0.1mol/L hydrochloric acid solution for later use.
2. Averagely dividing the derived standard substance into two parts, back-extracting one part with ethyl acetate, blowing nitrogen, measuring volume, detecting, and calculating the weight w of the derivative0(ii) a Extracting the other part with prepared solid phase micro extraction head of toothpick by shaking for 3 min, taking out the extraction head, extracting the rest solution with ethyl acetate, blowing nitrogen, measuring volume, detecting with computer, and calculating the weight w of derivative1. The adsorption rate k is calculated by the formula k ═ w0-w1)/w0×100％
The adsorption effect research shows that the adsorption rates of the toothpick solid-phase micro-extraction head prepared by the invention on four nitrofuran metabolite derivatives are respectively as follows: AMOZ (85%), AOZ (88%), AHD (83%), SEM (89%).
Example 3 Recycling of solid phase micro-extraction head of toothpick
1. Desorbing the treated sample with the marked toothpick solid phase micro-extraction head in ethyl acetate for 3 times, blowing nitrogen, performing constant volume, detecting on a machine, and researching the desorption and residue conditions of the toothpick solid phase micro-extraction head.
The result shows that the toothpick solid phase extraction head prepared by the invention has the desorption rate of 99% when desorbing once and the desorption rate of 100% when desorbing twice, and the target substance adsorbed by the extraction head can be completely desorbed through twice ethyl acetate elution, and finally no residue exists.
2. And (4) performing a sample labeling test on the treated toothpick solid-phase micro-extraction head again, and calculating the recovery rate.
To evaluate the reusability of the toothpick solid phase extraction head, 5 cycles of adsorption experiments were performed by analyzing pork supplemented with 40 μ L of NFs standard (concentration 0.1 μ g/mL). Each cycle was performed three times. The binding capacity for the target molecule for 5 cycles is shown in FIG. 9. During 5 cycles, each cycle was accompanied by a reduction in the chromatographic signal peak due to the decrease in adsorption capacity due to the loss of binding sites. After 5 cycles, the adsorption capacity of the SPME solid phase extraction head to 2-NP-AHD, 2-NP-AOZ and 2-NP-AMOZ is kept above 80%, and the adsorption capacity to 2-NP-SEM reaches above 50%. Based on the results, the toothpick solid phase extraction head shows good regeneration performance and can be recycled for a plurality of times.
Example 4 method for simply and rapidly detecting residual quantity of nitrofuran metabolites in chicken by using solid-phase microextraction head
1. Extraction step
Weighing 3g of a homogeneous sample (accurate to 0.01g) of chicken meat into a 50mL polypropylene centrifuge tube, adding 30 μ L of 0.1 μ g/mL internal standard working solution, adding 17mL of 0.125mol/L hydrochloric acid solution and 1.0mL of derivatization agent respectively, homogenizing for 1min, and placing in a constant temperature oscillator at 37 ℃ for 16 h. 10000r/min for 10min, taking 10mL of supernatant, adding 1mL of dipotassium phosphate solution, and adjusting the pH value to 7.0 by using 1mol/L sodium hydroxide solution and 0.1mol/L hydrochloric acid aqueous solution. Adding 5mL of normal hexane, vortex mixing for 2min to remove oil, centrifuging at 10000r/min for 10min, and discarding the normal hexane layer (aiming at a sample matrix with high fat content) to obtain the nitrofuran metabolite derivative solution.
2. Purification step
Putting the prepared solid-phase microextraction head into a nitrofuran metabolite derivative solution with the well-adjusted pH value (7.2-7.4), placing the solution in a constant-temperature oscillator at 37 ℃ at the rotation speed of 1800 rpm for vibration extraction for half an hour, taking out the toothpick solid-phase microextraction head, placing the toothpick solid-phase microextraction head into a centrifuge tube containing 5mL of water, placing the centrifuge tube in a constant-temperature oscillator at 37 ℃ at the rotation speed of 1800 rpm for vibration cleaning for 5 minutes, taking out the toothpick solid-phase microextraction head, placing the centrifuge tube containing 5mL of ethyl acetate, placing the centrifuge tube in a constant-temperature oscillator at 37 ℃ at the rotation speed of 1800 rpm for vibration desorption for half an hour, drying the toothpick solid-phase microextraction head at 50 ℃, using nitrogen for drying, fixing the volume to 0.5mL by using a mobile phase, filtering the solution into a sample bottle through a filter membrane of 0.2 mu m, and performing liquid-phase chromatography mass spectrometry.
3. Chromatographic assay conditions
A chromatographic column: ZORBAXeclipsePlusC18(1.8 μm, 2.1 x 50 mm); column temperature: 40 ℃, flow rate: 0.3ml/min, sample size: 10 mu L of the solution; mobile phase: a10mM ammonium acetate + 0.1% formic acid water, B methanol, gradient elution procedure: 0 → 3.0min, from 10% B → 90% B; 3.0 → 5.0min, 90% B; 5.0 → 6.5min, equilibrium from 90% B → 10% B, 1 min.
4. Conditions of Mass Spectrometry
An ionization mode: ESI +; the scanning mode is as follows: multiple Reaction Monitoring (MRM); electrospray voltage: 5500V; atomization gas pressure (GS 1): 55 psi; air curtain pressure (CUR): 35 psi; assist gas pressure (GS 2): 50 psi.
TABLE 2 Mass Spectrometry parameters for Nitrofuran metabolites and internal standards
*: and (4) quantifying ions.
5. Methodology validation
Taking the peak area ratio of the compound to be detected and an internal standard (shown in table 2) as a vertical coordinate and the marked concentration of the compound to be detected as a horizontal coordinate to perform linear regression analysis, and obtaining a linear regression equation, a correlation coefficient and a linear range, wherein the linear relation of the compounds is good and the r value of the correlation coefficient is more than 0.997 as shown in table 3.
TABLE 3 Linear Range, Linear equation and correlation coefficient for Nitrofuran metabolites
After different amounts of nitrofuran metabolite standard substances (the addition concentrations are 0.5 mug/kg, 2.5 mug/kg and 10 mug/kg) are added into chicken serving as a substrate, the nitrofuran metabolite standard substances are processed according to the methods of 1 and 2 and then are measured, the limit of quantitation is calculated according to a signal-to-noise ratio of 10 times, and the result is shown in a table 4.
TABLE 4 quantitation limit, recovery and precision
FIGS. 1-8 show chromatograms obtained by pre-treating chicken meat after adding 0.5 μ g/kg AMOZ, AOZ, AHD and SEM by a GB/T21311 and 2007 method developed by the invention, and the results are specifically as follows: the chromatographic peaks of the four nitrofuran metabolites obtained by the method have no obvious interferent, and particularly, when the AHD is detected by adopting a national standard method, an obvious interferent peak is near a target peak, but on an AHD chromatogram obtained by adopting the method developed by the invention, the impurity peak is removed, which is sufficient for the high selectivity of the solid phase extraction head developed by the invention to the AHD and the high-efficiency removal of the impurity interference. In addition, similar results were obtained for the detection of AOZ, and although the interference peak near the target was not removed, the impurity content was significantly reduced.
From the above studies, it can be seen that although the solid phase micro-extraction only adsorbs most of the target, and part of the target remains in the solution, the pretreatment according to the method of the present invention can reach or exceed the results obtained according to GB/T21311-2007 from the view point of the response value of the target near the limit of quantitation, and the limit of quantitation is far lower than the requirements specified in the countries such as European Union, Japan. The method mainly benefits from the high-efficiency adsorption and desorption capacity of developed toothpick solid phase micro-extraction on a target (the response value of the target is directly improved) and the excellent removal capacity of impurities, so that the influence of a matrix effect is reduced (the response value of the target is indirectly improved), particularly, the response value of AOZ pretreatment according to the national standard GB/T21311-2007 is about 5000cps, the response value of the pretreatment carried out by using the method developed by the invention can reach 15000cps, the impurity peak near the target is also reduced, and the quantitative limit of AOZ is improved by 3 to 4 times by using the method developed by the invention.
Claims (10)
1. The preparation method of the solid phase micro-extraction head is characterized by comprising the following steps:
dissolving polyacrylonitrile PAN powder in dimethylformamide, and stirring and dissolving at room temperature to obtain a saturated solution;
grinding the HLB particles to a preset particle size, adding the HLB particles into the PAN solution, and uniformly mixing to obtain PAN-HLB slurry;
fully shaking the obtained slurry at the rotating speed of 1800-;
fully shaking and cleaning the toothpick coated with the PAN-HLB slurry in a solvent solution at the rotating speed of 1500-1800 rpm to remove residues;
soaking the solid-phase micro-extraction head of the toothpick in a solvent with the volume ratio of 1: 1, activating HLB on the toothpick, and drying to obtain the solid phase micro-extraction head.
2. The production method according to claim 1, wherein the particle diameter of the HLB particle is 25 to 30 μm.
3. The method according to claim 1, wherein the content of the HLB particles in the PAN-HLB slurry is 0.025g to 0.075 g.
4. The production method according to claim 1, wherein the solvent solution is a mixed solution of methanol, isopropanol and acetonitrile in a volume ratio of 50:25: 25.
5. The solid phase microextraction head prepared by the preparation method according to any one of claims 1-4.
6. The use of the solid phase microextraction head according to claim 5 in the rapid detection of residual amount of nitrofurans metabolites in foods of animal origin.
7. The method for rapidly detecting the residual quantity of the nitrofurans metabolites in the foods of animal origin by using the solid phase microextraction head of claim 5 is characterized by comprising the following steps:
placing the prepared solid phase micro-extraction head into the nitrofuran metabolite derivative liquid containing the animal-derived food with the well-adjusted pH, placing the liquid in a constant temperature oscillator at 36-37 ℃, and performing oscillation extraction for 30-40min at the rotating speed of 1500-;
taking out the solid phase micro-extraction head, putting the solid phase micro-extraction head into a centrifuge tube filled with water, and placing the solid phase micro-extraction head into a constant temperature oscillator at 36-37 ℃ to shake and clean at the rotating speed of 1500-;
after the cleaning, taking out the solid phase micro-extraction head, putting the solid phase micro-extraction head into a centrifuge tube filled with ethyl acetate, and placing the solid phase micro-extraction head into a constant temperature oscillator at 36-37 ℃ to perform oscillation desorption for 30-40min at the rotating speed of 1500-;
and then blowing the mixture to be dry by nitrogen at the temperature of 45-50 ℃, metering the volume to 0.5mL by using a mobile phase, filtering the mixture into a sample bottle by using a 0.2-micrometer filter membrane, and measuring the residual quantity of the nitrofuran metabolites by adopting liquid chromatography-mass spectrometry.
8. The method of claim 7, wherein the chromatographic conditions of the liquid chromatography mass spectrometry are:
a chromatographic column: ZORBAXeclipsePlusC18(1.8 μm, 2.1 x 50 mm); column temperature: 40 ℃, flow rate: 0.3ml/min, sample size: 10 mu L of the solution; mobile phase: a: 10mM ammonium acetate + 0.1% formic acid water, B: methanol, gradient elution procedure: 0 → 3.0min, from 10% B → 90% B; 3.0 → 5.0min, 90% B; 5.0 → 6.5min, equilibrium from 90% B → 10% B, 1 min.
9. The method of claim 7, wherein the mass spectrometric conditions of the liquid chromatography mass spectrometry are:
an ionization mode: ESI+(ii) a The scanning mode is as follows: multiple Reaction Monitoring (MRM); electrospray voltage: 5500V; atomization gas pressure (GS 1): 55 psi; air curtain pressure (CUR): 35 psi; assist gas pressure (GS 2): 50 psi.
10. The method of claim 7, wherein the nitrofuran metabolite derived liquid comprising the food of animal origin is prepared by:
adding a homogeneous sample containing animal-derived food into a 50mL polypropylene centrifuge tube, adding 30 μ L of 0.1 μ g/mL internal standard working solution, then respectively adding 17mL of 0.125mol/L hydrochloric acid solution and 1.0mL of derivative, homogenizing for 1min, and placing in a constant-temperature oscillator at 36-37 ℃ for keeping for 16-17 h;
centrifuging at 10000r/min for 10min, taking 10mL of supernatant, adding 1mL of dipotassium phosphate solution, and adjusting the pH to 7.0 by using 1mol/L sodium hydroxide solution and 0.1mol/L hydrochloric acid aqueous solution;
then adding 5mL of normal hexane, vortex mixing for 2min to remove oil, centrifuging for 10min at 10000r/min, and discarding the normal hexane layer to obtain the nitrofuran metabolite derivative liquid containing animal-derived food.
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