CN113588822B - Solid phase microextraction head and preparation method and application thereof - Google Patents
Solid phase microextraction head and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a solid-phase microextraction head, a preparation method and application thereof, and belongs to the technical field of detection. The invention provides a novel concept of solid-phase microextraction, and a toothpick solid-phase microextraction head is developed based on the concept, which is an improvement and optimization of pretreatment technology in the process of detecting nitrofuran metabolite residues in animal-derived foods, and has the characteristics of no need of solvents, high extraction speed, good reproducibility, small sample consumption, simple and convenient operation, field analysis and the like. The solid-phase microextraction head provided by the invention has high-efficiency adsorption and desorption capacity for nitrofurans metabolites and excellent impurity removal capacity, can effectively improve the quantitative limit of nitrofurans metabolites, and has an effect obviously superior to that of national standard detection results.
Description
Technical Field
The invention belongs to the technical field of detection, and particularly relates to a solid-phase microextraction 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 (HPLC-MS/MS) for detecting the residual amount of nitrofuran drug metabolites in animal-derived foods of GB/T21311-2007, and liquid chromatography-tandem mass spectrometry for detecting the residual amount of nitrofuran metabolites in pork, beef, chicken, pork liver and aquatic products of GB/T20752-2006, wherein the methods in the above standards are high performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) and the common extraction and purification methods are liquid-liquid extraction and solid phase extraction.
However, for the above method, the range of the liquid-liquid extraction extract is wider, the total amount of the extracted substances is more, and the extremely complex sample can be interfered; moreover, the liquid-liquid extraction is finished manually, and automation cannot be realized. In addition, if pretreatment is performed by a solid-phase extraction method of liquid chromatography-tandem mass spectrometry for measuring residual amounts of nitrofurans metabolites in GB/T20752-2006 pork, beef, chicken, pork liver and aquatic products, the following disadvantages are also present: (1) the steps of pre-washing the column by methanol and water, passing the extracting solution through the column, washing impurities by water, eluting and the like are more complicated to operate; (2) the cost of the solid phase extraction column is high; (3) automation can be realized through a full-automatic solid phase extraction instrument, but the full-automatic solid phase extraction instrument is expensive and difficult to be equipped in a common laboratory; (4) the problems of easy blockage, difficult elution and the like of viscous and colloid complex samples exist.
Disclosure of Invention
The invention provides a solid-phase microextraction head, a preparation method and application thereof, and the obtained solid-phase microextraction head has high-efficiency adsorption and desorption capacity for nitrofurans metabolites and excellent impurity removal capacity, can effectively improve the quantitative limit of the nitrofurans metabolites, and has an effect obviously superior to the national standard detection result.
In order to achieve the above purpose, 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 HLB particles to a preset particle size, adding the ground HLB particles into PAN solution, and uniformly mixing to obtain PAN-HLB slurry;
the obtained slurry is fully vibrated at the rotating speed of 1800-2000 rpm, so that the particle mixture is uniformly distributed and then uniformly coated on the toothpick head;
fully vibrating and cleaning the toothpick coated with the PAN-HLB slurry in a solvent solution at a rotating speed of 1500-1800 rpm so as to remove residues;
immersing the toothpick solid phase microextraction head in a volume ratio of 1:1, activating the HLB on the dental stick, and drying to obtain the solid phase microextraction head.
The scheme of the invention provides a novel concept of solid-phase microextraction, 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, simple and convenient operation, field analysis and the like, and is an improvement and optimization of pretreatment technology in the detection process of nitrofuran metabolite residues in animal-derived foods. The HLB particles used in the above-described scheme are commercially available, for example, purchased from Waters company, and are a trade name of a solid phase extraction adsorbent, and a macroporous copolymer obtained by polymerizing two monomers of lipophilic divinylbenzene and hydrophilic N-vinylpyrrolidone in a certain ratio has a hydrophilic-lipophilic balance.
In particular, the Solid Phase Microextraction (SPME) technique employed in the present invention is significantly different from the existing Solid Phase Extraction (SPE) technique. Among these, SPE technology has three important processes: firstly, the sample passes through a solid adsorbent, and target analytes in the sample are completely extracted; secondly, eluting the interfering component from the adsorbent by using a leaching solvent; finally, the target analyte is eluted from the adsorbent using an eluting solvent. The SPE pursues absolute recovery of the target, and therefore, each step of the SPE has strict operating requirements. However, commercial SPE filling processes all use an excessive amount of filler, and the residual detection of most positive samples is at ppb level, which results in significant waste.
Unlike this, the SPME technique used in the present invention uses the principle of equilibrium extraction and selective adsorption to transfer the target analyte from the sample system to the coating, mainly in two steps: the first step is to expose the coating to the sample, whereby the analyte is selectively extracted due to the extremely strong affinity of the coating for the analyte; and in the second step, the extracted substances on the coating are desorbed. Because SPME does not need to completely adsorb the target, the relative recovery rate (realized by an internal standard method) is pursued, so that the operation steps are greatly simplified, the detection cost is reduced, and the detection time is greatly shortened.
Preferably, the HLB particles have a particle size of 25-30 μm. In a preferred embodiment, the HLB particles have a particle size of 30 μm. It will be appreciated that the HLB particle size at this size is selected because the HLB particle size significantly affects the ability to adsorb compounds to be tested and as the particle size increases, the adsorption factor increases (350-500).
Preferably, the PAN-HLB slurry has an HLB particle content of 0.025g to 0.075g. It will be appreciated that the content of HLB particles in the above slurry is limited with the aim that PAN acts as an adsorbent for HLB and toothpick, the ratio of which to the content of HLB significantly affects the preparation of SPME. If the PAN is too large in mass, the adsorption effect on target molecules is affected due to insufficient HLB ratio, and if the PAN is too large in mass, the PAN is difficult to adhere to the toothpick, so that the inventor obtains the optimal ratio through multiple experiments.
Preferably, the solvent solution is a mixed solution of methanol, isopropanol and acetonitrile, and the volume ratio of the solvent solution to the acetonitrile is 50:25:25.
The invention also provides a solid-phase microextraction head prepared by the preparation method according to any one of the technical schemes.
The invention also provides an application of the solid-phase microextraction head in the rapid detection of nitrofuran metabolite residual quantity in animal-derived foods.
The invention also provides a method for rapidly detecting the residual quantity of nitrofurans metabolites in animal-derived foods by using the solid-phase microextraction head according to the technical scheme, which comprises the following steps:
placing the prepared solid phase microextraction head into nitrofuran metabolite derivative liquid containing animal-derived food with adjusted pH, placing into a constant temperature oscillator at 36-37deg.C, and shake extracting at 1500-1800 rpm for 30-40min;
taking out the solid phase microextraction head, placing the solid phase microextraction head into a centrifuge tube filled with water, placing the centrifuge tube into a constant temperature oscillator at 36-37 ℃ and oscillating and cleaning the centrifuge tube at a rotating speed of 1500-1800 rpm;
after the cleaning is finished, the solid phase microextraction head is taken out and put into a centrifuge tube filled with ethyl acetate, and is placed into a constant temperature oscillator at 36-37 ℃ to be subjected to vibration desorption for 30-40min at a rotating speed of 1500-1800 rpm;
then drying with nitrogen at 45-50deg.C, fixing volume to 0.5mL with mobile phase, filtering with 0.2 μm filter membrane into sample bottle, and measuring nitrofuran metabolite residue by liquid chromatography mass spectrometry.
Preferably, the chromatographic measurement conditions for liquid chromatography mass spectrometry are:
chromatographic column: ZORBAXeclipse CalusC 18 (1.8 μm,2.1 x 50 mm); column temperature: 40 ℃, flow rate: sample injection amount of 0.3 ml/min: 10. Mu.L; mobile phase: a:10mM ammonium acetate+0.1% formic acid water, B: methanol;
gradient elution procedure: 0 to 3.0min, from 10% B to 90% B; 3.0.fwdarw.5.0 min,90% B;5.0 to 6.5min, equilibrated for 1min from 90% B to 10% B.
Preferably, the mass spectrometry conditions for liquid chromatography mass spectrometry are:
ionization mode: ESI (electronic service provider interface) + The method comprises the steps of carrying out a first treatment on the surface of the Scanning mode: multiple Reaction Monitoring (MRM); electrospray voltage: 5500V; atomization gas pressure (GS 1): 55psi; curtain air pressure (CUR): 35psi; auxiliary air pressure (GS 2): 50psi.
Preferably, the preparation method of the nitrofuran metabolite derivative liquid containing animal-derived food comprises the following steps:
adding a homogeneous sample containing animal-derived food into a 50mL polypropylene centrifuge tube, adding 30 mu L of 0.1 mu g/mL internal standard working solution, then respectively adding 17mL of 0.125mol/L hydrochloric acid solution and 1.0mL of derivatizing agent, homogenizing for 1min, and placing in a constant-temperature oscillator at 36-37 ℃ for 16-17h;
centrifuging at 10000r/min for 10min, collecting 10mL of supernatant, adding 1mL of dipotassium hydrogen phosphate solution, and adjusting pH to 7.0 with 1mol/L sodium hydroxide solution and 0.1mol/L hydrochloric acid aqueous solution;
then adding 5mL of n-hexane, vortex mixing for 2min for degreasing, centrifuging for 10min at 10000r/min, and discarding the n-hexane layer to obtain nitrofuran metabolite derivative liquid containing animal-derived food.
Compared with the prior art, the invention has the advantages and positive effects that:
1. according to the invention, the self-made solid-phase micro-extraction head is adopted to realize the rapid detection of the nitrofuran metabolite residue in animal-derived foods, 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. further, in the detection process, a vibration stirring mode is adopted to replace column passing, so that the problems that a viscous and colloidal complex sample is easy to block and difficult to elute are solved; meanwhile, the problem that the complex sample substrate liquid-liquid extraction purification effect is poor and interference possibly exists in the AHD detection process is also solved (see figure 9);
3. furthermore, the method provided by the invention can realize the semiautomatic treatment of mass adsorption, cleaning and desorption of the toothpick solid-phase microextraction head by means of constant-temperature oscillating water bath used in derivatization without purchasing an expensive full-automatic solid-phase extractor, thereby greatly improving the treatment efficiency.
Drawings
FIG. 1 is a chromatogram of 0.5 μg/kg chicken addition recovery AMOZ as determined using the method in GB/T21311-2007;
FIG. 2 is a chromatogram of 0.5 μg/kg chicken addition recovery AMOZ provided by an embodiment of the present invention;
FIG. 3 is a graph of 0.5 μg/kg chicken addition recovery AOZ as determined by the method of GB/T21311-2007;
FIG. 4 is a graph of 0.5 μg/kg chicken add recovery AOZ provided by an embodiment of the present invention;
FIG. 5 is a chromatogram of 0.5 μg/kg chicken addition recovery AHD as determined using the method in GB/T21311-2007;
FIG. 6 is a chromatogram of 0.5 μg/kg chicken addition recovery AHD provided by an embodiment of the invention;
FIG. 7 is a SEM chromatogram of 0.5 μg/kg chicken addition recovery as determined by the method of GB/T21311-2007;
FIG. 8 is a SEM chromatogram of 0.5 μg/kg chicken addition recovery provided by an embodiment of the invention;
FIG. 9 shows the recycling of the toothpick solid phase extraction head developed by the invention.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The names and abbreviations of the four nitrofuran metabolites involved in the invention are shown in Table 1:
TABLE 1 names and abbreviations for four nitrofuran metabolites
Example 1 preparation method of toothpick solid phase microextraction head
1. 7g of PAN powder was dissolved in 100mL of Dimethylformamide (DMF) and stirred continuously at room temperature to ensure uniform dissolution.
2. Oasis HLB particles (30 μm) were milled using a ball mill at 240rpm for 2 hours.
3. 1g HLB was mixed with 10mL PAN solution to obtain the final PAN-HLB slurry. The mixture was then homogenized on a shaker at 1800 rpm for 12 hours to provide a sufficiently homogeneous mixture of particles.
4. Dipping the PAN-HLB slurry with a toothpick with a length of about 1cm to uniformly coat the toothpick with the slurry, dipping and coating once after slightly drying,
5. the toothpick was rinsed twice (methanol, isopropanol and acetonitrile (MeOH/IPA/ACN, 50:25:25) in solvent solution with shaking at 1500 rpm for a total of 15 minutes to remove residue.
6. Pretreating toothpick solid phase microextraction head with methanol/water mixture (MeOH/H) 2 O, 50:50), activating HLB on the dental swab, and airing for later use.
EXAMPLE 2 adsorption Effect study of toothpick solid phase microextraction head
1. The nitrofuran metabolite standard substance with a certain concentration is derived, and specifically comprises the following components:
200 mu L of working solution of 4 nitrofuran metabolites with the concentration of 0.1 mu g/mL are taken, 17mL of hydrochloric acid solution with the concentration of 0.125mol/L and 1.0mL of 2-nitrobenzaldehyde are respectively added, the solution is placed in a constant temperature oscillator for derivatization reaction for 16 hours at 37 ℃, 1mL of dipotassium hydrogen phosphate solution is added, and pH value between 7.2 and 7.4 is regulated by 1mol/L of sodium hydroxide solution and 0.1mol/L of hydrochloric acid aqueous solution for standby.
2. Dividing the derived standard product into two parts, reversely extracting one part by ethyl acetate, blowing nitrogen, detecting by a machine after constant volume, and calculating the mass w of the derivative 0 The method comprises the steps of carrying out a first treatment on the surface of the The other part is subjected to vibration extraction and adsorption for 3 minutes by using the prepared toothpick solid-phase microextraction head, the residual liquid is subjected to back extraction by using ethyl acetate after the extraction head is taken out, nitrogen blowing is performed, and the machine detection is performed after the constant volume is performed, wherein the mass w of the derivative is calculated 1 . The adsorption rate k is calculated, and the formula is k= (w 0- w 1 )/w 0 ×100％
Adsorption effect researches show that the adsorption rates of the toothpick solid-phase microextraction 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 study of toothpick solid phase microextraction head
1. Desorbing the treated sample with the labeled toothpick solid phase microextraction head in ethyl acetate for 3 times, blowing nitrogen, and detecting by a machine after constant volume to study the desorption and residual condition of the toothpick solid phase microextraction head.
The result shows that the desorption rate of the toothpick solid phase extraction head prepared by the invention is 99% when the toothpick solid phase extraction head is desorbed once, the desorption rate reaches 100% when the toothpick solid phase extraction head is desorbed twice, and all target substances adsorbed by the toothpick solid phase extraction head can be desorbed through eluting with ethyl acetate twice, so that no residue exists finally.
2. And (5) carrying out a sample marking test again on the treated toothpick solid-phase microextraction head, and calculating the recovery rate.
To evaluate the reusability of the toothpick solid phase extraction head, an adsorption experiment was performed for 5 cycles by analyzing pork with 40. Mu.L NFs standard (0.1. Mu.g/mL concentration). Each cycle was performed three times. The binding capacity of 5 cycles to the target molecule is shown in FIG. 9. During the 5 cycles, each cycle was accompanied by a decrease in the peak of the chromatographic signal due to a 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 maintained to be more than 80%, and the adsorption capacity to 2-NP-SEM is maintained to be more than 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 simple and rapid detection of residual amount of nitrofurans metabolite in chicken by solid-phase microextraction head
1. Extraction step
A homogeneous sample of 3g chicken (accurate to 0.01 g) was weighed into a 50mL polypropylene centrifuge tube, 30. Mu.L of 0.1. Mu.g/mL of an internal standard working solution was added, 17mL of 0.125mol/L hydrochloric acid solution and 1.0mL of a derivatizing agent were added, homogenized for 1min, and placed in a constant temperature shaker at 37℃for 16h. Centrifugation at 10000r/min for 10min, 10mL of the supernatant was taken, 1mL of dipotassium hydrogen phosphate solution was added, and pH7.0 was adjusted with 1mol/L sodium hydroxide solution and 0.1mol/L aqueous hydrochloric acid solution. Adding 5mL of n-hexane, vortex mixing for 2min to remove oil, centrifuging for 10min at 10000r/min, and discarding n-hexane layer (aiming at sample matrix with high fat content) to obtain nitrofuran metabolite derivative liquid.
2. Purification step
Placing the prepared solid-phase microextraction head into nitrofuran metabolite derivative liquid with the pH value adjusted (7.2-7.4), placing the nitrofuran metabolite derivative liquid into a constant-temperature oscillator with the temperature of 37 ℃ for shaking and extracting for half an hour at the speed of 1800 revolutions per minute, taking out the toothpick solid-phase microextraction head, placing the toothpick solid-phase microextraction head into a centrifuge tube containing 5mL of ethyl acetate at the temperature of 37 ℃ for shaking and desorbing for half an hour at the speed of 1800 revolutions per minute, drying by nitrogen, fixing the volume to 0.5mL by mobile phase, filtering the sample bottle by a filter membrane with the volume of 0.2 mu m, and measuring by liquid chromatography mass spectrometry.
3. Chromatographic measurement conditions
Chromatographic column: ZORBAXeclipse CalusC 18 (1.8 μm,2.1 x 50 mm); column temperature: 40 ℃, flow rate: sample injection amount of 0.3 ml/min: 10. Mu.L; mobile phase: a10mM ammonium acetate +0.1% formic acid water, B methanol, gradient elution procedure: 0 to 3.0min, from 10% B to 90% B; 3.0.fwdarw.5.0 min,90% B;5.0 to 6.5min, equilibrated for 1min from 90% B to 10% B.
4. Mass spectrometry conditions
Ionization mode: esi+; scanning mode: multiple Reaction Monitoring (MRM); electrospray voltage: 5500V; atomization gas pressure (GS 1): 55psi; curtain air pressure (CUR): 35psi; auxiliary air pressure (GS 2): 50psi.
TABLE 2 Mass Spectrometry parameters for nitrofuran metabolites and internal standards
* : and quantifying ions.
5. Methodological verification
And (3) carrying out linear regression analysis by taking the peak area ratio of the compound to be detected and an internal standard (shown in table 2) as an ordinate and the marked concentration of the compound to be detected as an abscissa to obtain a linear regression equation, a correlation coefficient and a linear range, wherein the linear relation of each compound is good, and the value of the correlation coefficient r is larger than 0.997 as shown in table 3.
TABLE 3 Linear Range, linear equation and correlation coefficient of nitrofuran metabolites
Different amounts (0.5. Mu.g/kg, 2.5. Mu.g/kg, 10. Mu.g/kg) of nitrofuran metabolite standard were added using chicken as substrate, and the quantitative limit was calculated from the 10-fold signal to noise ratio as determined after treatment according to the methods described in "1, 2", and the results are shown in Table 4.
TABLE 4 quantitative limit, recovery and precision
FIGS. 1-8 show chromatograms obtained by pretreatment of chicken with the GB/T21311-2007 method and the method developed by the present invention after addition of 0.5 μg/kg AMOZ, AOZ, AHD and SEM, respectively, with the results specifically being: the chromatographic peaks of the four nitrofuran metabolites obtained by the method have no obvious interference substances, and particularly, when the national standard method is adopted for AHD detection, the obvious interference peak exists near the target peak, but the impurity peak is removed on the AHD chromatogram obtained by the method, so that the high selectivity of the solid phase extraction head developed by the invention to AHD and the high efficiency of impurity interference removal are enough. In addition, similar results are obtained for AOZ detection, but the impurity content is significantly reduced, although the interference peaks near the target are not removed.
As can be seen from the above study, although solid phase microextraction only adsorbs most of the target, and part of the target remains in solution, from the response value of the target near the limit of quantification, the pretreatment according to the method developed by the invention can reach or be better than the result obtained according to national standard GB/T21311-2007, and the limit of quantification is far lower than the requirements specified by the countries of European Union, japan and the like. The method mainly benefits from the high-efficiency adsorption and desorption capability of the developed toothpick solid-phase microextraction on the target (directly improves the response value of the target) and the excellent removal capability of impurities, so that the influence of matrix effect is reduced (indirectly improves the response value of the target), and particularly the response value of AOZ pretreatment according to national standard GB/T21311-2007 is about 5000cps, the response value of the pretreatment can reach 15000cps by utilizing the method developed by the invention, and the impurity peak near the target is reduced, and the quantitative limit of the AOZ is improved by 3 to 4 times by utilizing the method developed by the invention.
Claims (5)
1. The application of the solid-phase microextraction head in the rapid detection of the residual quantity of nitrofurans metabolites in animal-derived foods is characterized in that the solid-phase microextraction head is prepared by the following steps:
dissolving polyacrylonitrile PAN powder in dimethylformamide, and stirring and dissolving at room temperature to obtain a saturated solution;
grinding HLB particles to 25-30 μm, adding into PAN solution, and mixing to obtain PAN-HLB slurry, wherein the content of HLB particles is 0.025-0.075 g;
the obtained slurry is fully vibrated at the rotating speed of 1800-2000 rpm, so that the particle mixture is uniformly distributed and then uniformly coated on the toothpick head;
fully vibrating and cleaning the toothpick coated with the PAN-HLB slurry in a solvent solution at a rotating speed of 1500-1800 rpm so as to remove residues;
immersing the toothpick solid phase microextraction head in a volume ratio of 1:1, pre-treating the mixture of methanol and water, activating the HLB on the dental stick, and drying to obtain a solid-phase microextraction head;
the detection comprises the following steps:
placing the prepared solid phase microextraction head into nitrofuran metabolite derivative liquid containing animal-derived food with adjusted pH, placing into a constant temperature oscillator at 36-37deg.C, and shake extracting at 1500-1800 rpm for 30-40min;
taking out the solid phase microextraction head, placing the solid phase microextraction head into a centrifuge tube filled with water, placing the centrifuge tube into a constant temperature oscillator at 36-37 ℃ and oscillating and cleaning the centrifuge tube at a rotating speed of 1500-1800 rpm;
after the cleaning is finished, the solid phase microextraction head is taken out, put into a centrifuge tube filled with ethyl acetate, and put into a constant temperature oscillator at 36-37 ℃ to be subjected to vibration desorption for 30-40min at a rotating speed of 1500-1800 rpm;
drying with nitrogen at 45-50deg.C, fixing volume to 0.5mL with mobile phase, filtering with 0.2 μm filter membrane into sample bottle, and measuring nitrofuran metabolite residue by liquid chromatography mass spectrometry.
2. The use 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.
3. The use according to claim 1, wherein the chromatographic conditions of the liquid chromatographic mass spectrometry are:
chromatographic column: ZORBAXeclipse CalusC 18; column temperature: 40 ℃, flow rate: sample injection amount of 0.3 ml/min: 10. Mu.L; mobile phase: a:10mM ammonium acetate+0.1% formic acid water, B: methanol, gradient elution procedure: 0 to 3.0min, from 10% B to 90% B; 3.0.fwdarw.5.0 min,90% B;5.0 to 6.5min, equilibrated for 1min from 90% B to 10% B.
4. The use according to claim 1, wherein the mass spectrometry conditions of the liquid chromatography mass spectrometry are:
ionization mode: esi+; scanning mode: multiple Reaction Monitoring (MRM); electrospray voltage: 5500V; atomization gas pressure (GS 1): 55psi; curtain air pressure (CUR): 35psi; auxiliary air pressure (GS 2): 50psi.
5. The use according to claim 1, characterized in that the preparation method of nitrofuran metabolite derivative liquid containing animal-derived food is:
adding a homogeneous sample containing animal-derived food into a 50mL polypropylene centrifuge tube, adding 30 mu L of 0.1 mu g/mL internal standard working solution, then respectively adding 17mL of 0.125mol/L hydrochloric acid solution and 1.0mL of derivatizing agent, homogenizing for 1min, and placing in a constant-temperature oscillator at 36-37 ℃ for 16-17h;
centrifuging at 10000r/min for 10min, collecting 10mL of supernatant, adding 1mL of dipotassium hydrogen phosphate solution, and adjusting pH to 7.0 with 1mol/L sodium hydroxide solution and 0.1mol/L hydrochloric acid aqueous solution;
then adding 5mL of n-hexane, vortex mixing for 2min for degreasing, centrifuging for 10min at 10000r/min, and discarding the n-hexane layer to obtain nitrofuran metabolite derivative liquid containing animal-derived food.
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| US9625426B2 (en) * | 2015-03-04 | 2017-04-18 | Janusz Pawliszyn | Standard analyte generator |
| EP3423808B1 (en) * | 2016-03-02 | 2023-08-16 | JP Scientific Limited | Method and instrument for extracting a component from a sample |
| CN110308014A (en) * | 2019-06-20 | 2019-10-08 | 华中师范大学 | A kind of in-situ self-sealing solid-phase microextraction sampler and operation method thereof |
| CN110361462B (en) * | 2019-06-21 | 2020-07-31 | 深圳市检验检疫科学研究院 | Molecularly imprinted tube tip micro-extraction head and preparation method thereof |
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| WO2015188283A1 (en) * | 2014-06-13 | 2015-12-17 | Pawliszyn Janusz B | A probe for extraction of molecules of interest from a sample |
| CN110470763A (en) * | 2019-08-23 | 2019-11-19 | 北京六角体检测技术有限公司 | Method that is a kind of while detecting aquatic products Malachite Green, metabolites of nitrofuran and chloramphenicol residue |
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