CN106226424B - A kind of method of magnetic graphene Solid Phase Extraction combination LC-MS instrument detection meat products veterinary drug residue - Google Patents
A kind of method of magnetic graphene Solid Phase Extraction combination LC-MS instrument detection meat products veterinary drug residue Download PDFInfo
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- CN106226424B CN106226424B CN201610556009.XA CN201610556009A CN106226424B CN 106226424 B CN106226424 B CN 106226424B CN 201610556009 A CN201610556009 A CN 201610556009A CN 106226424 B CN106226424 B CN 106226424B
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Abstract
The present invention provides a kind of methods of magnetic graphene Solid Phase Extraction combination LC-MS instrument detection meat products veterinary drug residue, and the method includes first carrying out Solid Phase Extraction by adsorbent of magnetic graphene, then carry out HPLC-MS/MS measurement analysis again.The method is easy to operate, rapidly and efficiently, has greatly saved the time of sample pre-treatments；Solid Phase Extraction is carried out by adsorbent of magnetic graphene, save the cost, the rate of recovery is high, it measures and analyzes then in conjunction with HPLC-MS/MS, the retention time and molecular structure information of target compound, high sensitivity can be provided simultaneously, and quantitative analysis and qualitative confirmation can be carried out, have many advantages, such as reproducible, good operability, simple, economic, is suitable for routine testing.
Description
Technical field
The present invention relates to a kind of detection methods of meat products veterinary drug residue, and in particular to one kind is to inhale with magnetic graphene
Attached dose of Solid Phase Extraction combination LC-MS instrument belongs to food safety detection technology come the method for detecting meat products veterinary drug residue
Field.
Background technique
In the prior art for the detection of meat products veterinary drug residue, require to carry out sample pre-treatments, and before sample
Reason is the committed step eliminated matrix interference, protect instrument, mainly includes the processes such as extracting and developing, purification, concentration, can be effective
Accuracy, precision and the sensitivity of improvement method.In general, sample pre-treatments account for about more than half of entire analysis time, it is
The entire key of analyte detection process and one of the difficult point of food safety detection and hot issue.
In recent years, new method, the new technology being generally concerned in sample pre-treatments mainly have gel permeation chromatography, accelerate
Solvent extraction, the extraction of microwave-assisted solvent and Solid Phase Extraction.Gel permeation chromatography is suitable for rich in macromoleculars such as fat, pigments
Sample；Accelerated solvent extractor is widely used in the analysis of the sample pretreatment process in each field, especially pesticide residue, but by
Expensive in the equipment price of this method, application is subject to certain restrictions；Microwave-assisted solvent extraction is mainly used for extracting plant
In natural component；Adsorbent material used by Solid Phase Extraction has carbon nanotube, active carbon, C18 silica gel etc., due to these absorption
The limited sorption capacity of material causes its extraction efficiency low, increases the usage amount of solvent, increases processing cost, and time-consuming,
Lead to accuracy, precision and the sensitivity decrease of subsequent analysis testing result.
Summary of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of magnetic graphene Solid Phase Extraction combination LC-MS
The method that instrument detects meat products veterinary drug residue first carries out Solid Phase Extraction by adsorbent of magnetic graphene, then carries out again
HPLC-MS/MS measurement analysis, this method have the characteristics that at low cost, easy to operate, time-consuming short, favorable reproducibility.
A kind of method of magnetic graphene Solid Phase Extraction combination LC-MS instrument detection meat products veterinary drug residue, the side
Method includes first carrying out Solid Phase Extraction by adsorbent of magnetic graphene, then carries out HPLC-MS/MS measurement analysis again；
The veterinary drug is adamantane compound or carbadox class compound or sulfonamides compound or uracil class
Close object or one or more of carbostyril compound or macrolides compound；
The magnetic graphene is combined by graphene and magnetic nano-particle, and the magnetic graphene is commercially available production
Product are purchased in Nanjing Xian Feng Nono-material Science & Technology Ltd..
Why the present invention uses magnetic graphene to carry out pre-treatment as adsorbent, is selected according to the property of sample
It selects, because impurity in the sample is mainly pigment, grease, polarity and the non-targeted compound of nonpolarity, and magnetic graphene
Specific surface area it is larger, can effectively adsorb these impurity, reduce matrix interference effect, improve the target compound rate of recovery.Due to
Sample pre-treatments are one of the key points tested and analyzed, thus it is only that sample treatment is good, it can just effectively improve detection method
Accuracy, precision and sensitivity, the present invention carry out pre-treatment as adsorbent using magnetic graphene, and extraction efficiency is high, greatly
Reduce the use of solvent greatly, time-consuming is reduced, and greatly reduces processing cost.
A kind of method of magnetic graphene Solid Phase Extraction combination LC-MS instrument detection meat products veterinary drug residue is specific to walk
Suddenly include:
(1) configuration of standard solution
The configuration of Standard Stock solutions: accurately weighing each standard items and dissolve and be settled to 100mL with acetonitrile or methanol respectively,
It mixes, is configured to concentration and is the Standard Stock solutions of 100 μ g/mL, and the solution is placed in 0~4 DEG C of refrigerator and is saved；
The configuration of intermediate standard stock solution: accurately pipetting above-mentioned each Standard Stock solutions, fixed with acetonitrile or methanol respectively
Hold to 100mL, mix, is configured to the intermediate standard stock solution that concentration is 1.0 μ g/mL；
(2) preparation of sample to be tested
Sample segment is taken out from taken original meat sample product, smashs to pieces uniformly, mixes well through high-speed tissue mashing machine, with four
Point-score division goes out the sample to be tested of no less than 200g, is packed into cleaning container, after sealing up, shows to mark, be put into refrigerator；
(3) it purifies
Take above-mentioned sample to be tested, thaw, accurately weigh 2.00 scholar 0.02g and be placed in 50mL centrifuge tube, be added 2mL water and
Then 4.0g anhydrous magnesium sulfate and 1.0g sodium chloride is added in 10mL acetonitrile/methanol (80/20, v/V), homogenizer homogeneous 2min, then
Vortex oscillation extracts 2min, and 5000r/min is centrifuged 10min, obtains supernatant；
(4) it extracts
10mg magnetic graphene and 150mg anhydrous magnesium sulfate are weighed in 50mL centrifuge tube, above-mentioned supernatant is added, is placed in
2min is vibrated on oscillator, then magnetic graphene is gathered into centrifugation bottom of the tube with magnet, and supernatant is transferred to 10mL centrifuge tube
In, it is dried with nitrogen, mobile phase is settled to 1mL, crosses 0.22 μm of filter membrane, then carry out HPLC-MS/MS measurement analysis；
The veterinary drug is amantadine or trichomonas net or sulphadiazine or sulphathiazole or ayerlucil or methoxy benzyl
Pyridine or Ciprofloxacin or Enrofloxacin or one or more of Ofloxacin or Tilmicosin, the veterinary drug purity are all larger than
98%, buying is in Sigma Co., USA.
Amantadine, also known as 1- amantadine, molecular formula C10H17N, No. CAS is 768-94-5, belongs to adamantane
Close object；
Trichomonas net also known as mequindox, 3- methyl -2- acetyl group-Isosorbide-5-Nitrae-dioxy quinoline, No. CAS is 16915-79-0, point
Minor is C10H10N2O3, belong to carbadox class compound；
Sulphadiazine, molecular formula C10H10N4O2S CAS is 68-35-9；Sulphathiazole, molecular formula C9H9N3O2S2No. CAS
For 72-14-0；Ayerlucil, molecular formula C9H10N4O2S CAS is 144-82-1；Belong to sulfonamides compound；
Trimethoprim also known as methoxybenzyl aminopyrimidine, No. CAS is 738-70-5, belongs to diaminopyrimidine class compound；Molecular formula
C14H18N4O3
Ciprofloxacin molecular formula C17H18FN3O3, Enrofloxacin molecular formula C19H22FN3O3With Ofloxacin molecular formula
C18H20FN3O4, belong to carbostyril compound；
Tilmicosin molecular formula C46H80N2O13, belong to macrolides compound.
The condition of the HPLC-MS/MS measurement analysis are as follows:
Chromatographic column: ZORBAX Eclipse Plus C18,1.8 μm, 3.0 × 100mm；Column temperature: 40 DEG C；Sample volume: 20 μ
L；Mobile phase: the aqueous formic acid that A volume fraction is 0.1%, B acetonitrile；HPLC gradient elution condition are as follows:
Ion source: electric spray ion source；Scanning mode: cation scanning；Detection mode: multiple reaction monitoring；Ion source
Temperature (GAS Temp): 350 DEG C；Gas flow rate (GAS Flow): 10L/min；Nebulizer pressure (Nebulizer): 40psi.
The mass spectrometry parameters of the veterinary drug:
In view of analysis veterinary drug as described herein is measured simultaneously, so being selected in HPLC-MS/MS measurement analytic process
Column length is 3.0 × 100mm C18 chromatographic column, while selecting the filler of 1.8um, so that the surface area in cylinder unit volume is significantly
Increase, column effect significantly improves；And according to the property of veterinary drug described herein, using 0.3mL/min column flow rate and electron spray from
The flow velocity of sub-ization mode has good matching, further effectively improves accuracy, precision and the sensitivity of detection method.
Equipment of the present invention is commercial equipment.
The meat products is one kind of chicken or pork.
Anhydrous magnesium sulfate described in step (3) and sodium chloride are added in solid form, and anhydrous magnesium sulfate, which rises, to be inhaled
Water effect, sodium chloride play salting out.
Anhydrous magnesium sulfate described in step (4) is added in solid form, and anhydrous magnesium sulfate plays water sorption.
The revolving speed of homogenizer described in step (3) is 10000 turns/min.
Mobile phase described in step (4) is acetonitrile/aqueous formic acid, 20%V/80%V, wherein formic acid in aqueous formic acid
Volume fraction be 0.1%.
The method of magnetic graphene Solid Phase Extraction combination LC-MS instrument detection meat products veterinary drug residue of the present invention,
The method includes first carrying out Solid Phase Extraction by adsorbent of magnetic graphene, then carry out HPLC-MS/MS measurement analysis again.
Compared with prior art, (1) uses magnetic graphene to carry out Solid Phase Extraction for adsorbent to the method, easy to operate, quickly high
Effect, has greatly saved the time of sample pre-treatments；(2) magnetic graphene can recycle benefit as adsorbent after over cleaning
With save the cost；(3) Solid Phase Extraction is carried out by adsorbent of magnetic graphene, the rate of recovery is high, surveys then in conjunction with HPLC-MS/MS
Setting analysis can provide the retention time and molecular structure information of target compound, high sensitivity simultaneously, and can be determined
Amount analysis and qualitative confirmation, have many advantages, such as reproducible, good operability, simple, economic, are suitable for routine testing.
Detailed description of the invention
Fig. 1 is the mass spectrogram of veterinary drug sample amantadine of the present invention；
Fig. 2 is the mass spectrogram of veterinary drug sample trichomonas net of the present invention；
Fig. 3 is the mass spectrogram of veterinary drug sample sulphadiazine of the present invention；
Fig. 4 is the mass spectrogram of veterinary drug sample sulphathiazole of the present invention；
Fig. 5 is the mass spectrogram of veterinary drug sample ayerlucil of the present invention；
Fig. 6 is the mass spectrogram of veterinary drug sample trimethoprim of the present invention；
Fig. 7 is the mass spectrogram of veterinary drug sample Ciprofloxacin of the present invention；
Fig. 8 is the mass spectrogram of veterinary drug sample Enrofloxacin of the present invention；
Fig. 9 is the mass spectrogram of veterinary drug sample Ofloxacin of the present invention；
Figure 10 is the mass spectrogram of veterinary drug sample Tilmicosin of the present invention；
All detections of the present invention are completed in Weifang Entry-Exit Inspection and Quarantine Bureau.
Specific embodiment
Embodiment 1
Sample source: it is purchased from Weifang City and goes down south 5 parts of Fresh Grade Breast of river market freezing, every part of 500g.It is smash respectively through high-speed organization
Broken machine is smashed to pieces uniformly, is mixed well.
(1) preparation of standard solution
10 kinds of veterinary drug standard reserving solutions are diluted to the standard working solution of respective concentration, are shown in Table 1.
The standard concentration gradient table of each compound of table 1
(2) it extracts
Take above-mentioned sample to be tested, thaw, accurately weigh 2.00 scholar 0.02g and be placed in 50mL centrifuge tube, be added 2mL water and
Then 4.0g anhydrous magnesium sulfate and 1.0g sodium chloride is added in 10mL acetonitrile/methanol (80/20, v/v), homogenizer homogeneous 2min, then
Vortex oscillation extracts 2min, and 5000r/min is centrifuged 10min, obtains supernatant；
(3) it purifies
10mg magnetic graphene and 150mg anhydrous magnesium sulfate are weighed in 50mL centrifuge tube, above-mentioned supernatant is added, is placed in
2min is vibrated on oscillator, then magnetic graphene is gathered into centrifugation bottom of the tube with magnet, and supernatant is transferred to 10mL centrifuge tube
In, it is dried with nitrogen, mobile phase is settled to 1mL, crosses 0.22 μm of filter membrane, then carry out HPLC-MS/MS measurement analysis；
(4) liquid phase chromatogram condition
Chromatographic column: ZORBAX Eclipse Plus C18,1.8 μm, 3.0 × 100mm；Column temperature: 40 DEG C；Sample volume: 20 μ
L；Mobile phase: the aqueous formic acid that A volume fraction is 0.1%, B acetonitrile；HPLC gradient elution condition are as follows:
| Time (min) | Flow velocity (μ L/min) | A (%) | B (%) |
| 0.00 | 300 | 90 | 10 |
| 3.00 | 300 | 70 | 30 |
| 7.00 | 300 | 20 | 80 |
| 7.1 | 300 | 90 | 10 |
| 10.0 | 300 | 90 | 10 |
(5) Mass Spectrometry Conditions
Ion source: electric spray ion source；Scanning mode: cation scanning；Detection mode: multiple reaction monitoring；GAS
Temp:350 DEG C；GAS Flow:10L/min；Nebulizer:40psi；The mass spectrometry parameters of the veterinary drug:
As a result with analysis
The range of linearity, quantitative limit, the rate of recovery and precision
A series of compound mixed standard solution of various concentrations is prepared with matrix extracting solution, successively sample introduction, with response peak
Area be ordinate Y, to respective concentration X (μ g/kg) carry out linear regression analysis, by work station can directly calculate regression equation and
Related coefficient is shown in Table 2.10 kinds of veterinary drugs linear relationship within the scope of 5-80 μ g/kg is good, and related coefficient is all larger than
0.9950, the standard curve is reliable.The rate of recovery and Precision Experiment are carried out with blank sample mark-on method.Chicken is carried out respectively
The mark-on of three different levels, each horizontal parallel measure 6 times, calculate the rate of recovery and relative standard deviation, the results are shown in Table 2.From
Table 2 is as can be seen that various compounds are in L1, and L3, the rate of recovery of L5 mark-on level is between 73.9%~112.8%, opposite mark
Quasi- deviation (RSD) is between 10.3%~13.7%.
2 chicken of table adds the average recovery rate (matrix correction and standard items) and precision (matrix correction) of sample
Qualitative and quantitative detection is carried out to commercially available 5 parts of chicken meat samples using the method that this experiment is established, each sample is pressed
Sample pre-treatments are carried out according to the above method, it is quantitative using matrix matching calibration curve later using HPLC-MS/MS measurement analysis
It calculates.The results show that have micro medicament residue detection, respectively Tilmicosin and Enrofloxacin there are two only in sample,
It is remaining to be not detected.
Embodiment 2
Sample source: it is purchased from Weifang City and goes down south 5 parts of river market raw pork, every part of 500g.Respectively through high-speed tissue mashing machine
It smashs to pieces uniformly, mixes well.
It is carried out by step described in embodiment 1.
As a result with analysis
The range of linearity, quantitative limit, the rate of recovery and precision
A series of compound mixed standard solution of various concentrations is prepared with matrix extracting solution, successively sample introduction, with response peak
Area be ordinate Y, to respective concentration X (μ g/kg) carry out linear regression analysis, by work station can directly calculate regression equation and
Related coefficient is shown in Table 3.10 kinds of veterinary drugs linear relationship within the scope of 5-80 μ g/kg is good, and related coefficient is all larger than
0.9960, the standard curve is reliable.The rate of recovery and Precision Experiment are carried out with blank sample mark-on method.Respectively to raw pork into
The mark-on of three different levels of row, each horizontal parallel measure 6 times, calculate the rate of recovery and relative standard deviation, the results are shown in Table 3.
From table 3 it can be seen that various compounds are in L1, L3, the rate of recovery of L5 mark-on level is between 80.5%~100.8%, relatively
Standard deviation (RSD) is between 7.3%~12.7%.3 raw pork of table adds average recovery rate (matrix correction and the standard of sample
Product) and precision (matrix correction)
Qualitative and quantitative detection is carried out to commercially available 5 parts of raw pork samples using the method that this experiment is established, each sample is equal
Sample pre-treatments are carried out according to the method described above, it is fixed using matrix matching calibration curve later using HPLC-MS/MS measurement analysis
Amount calculates.The results show that 10 kinds of drugs are not detected.
Claims (5)
1. a kind of method of magnetic graphene Solid Phase Extraction combination LC-MS instrument detection meat products veterinary drug residue, feature exist
In: the method includes first carrying out Solid Phase Extraction by adsorbent of magnetic graphene, then carry out HPLC-MS/MS measurement point again
Analysis；
The magnetic graphene is combined by graphene and magnetic nano-particle；
Specific steps include:
(1) configuration of standard solution
The configuration of Standard Stock solutions: accurately weighing each standard items and dissolve and be settled to 100mL with acetonitrile respectively, mixes, configuration
The Standard Stock solutions for being 100 μ g/mL at concentration, and the solution is placed in 0~4 DEG C of refrigerator and is saved；
The configuration of intermediate standard stock solution: accurately pipetting above-mentioned each Standard Stock solutions, be settled to 100mL with acetonitrile respectively,
It mixes, is configured to the intermediate standard stock solution that concentration is 1.0 μ g/mL；
(2) preparation of sample to be tested
Sample segment is taken out from taken original meat sample product, smashs to pieces uniformly, mixes well through high-speed tissue mashing machine, use quartering
Division goes out the sample to be tested of no less than 200g, is packed into cleaning container, after sealing up, shows to mark, be put into refrigerator；
(3) it extracts
Above-mentioned sample to be tested is taken, is thawed, is accurately weighed 2.00 scholar 0.02g and be placed in 50mL centrifuge tube, 2mL water and 10mL second is added
Nitrile/methanol, acetonitrile: then 4.0g anhydrous magnesium sulfate and 1.0g chlorination is added in methanol=80:20V/V, homogenizer homogeneous 2min
Sodium, then vortex oscillation extract 2min, and 5000r/min is centrifuged 10min, obtains supernatant；
(4) it purifies
10mg magnetic graphene and 150mg anhydrous magnesium sulfate are weighed in 50mL centrifuge tube, above-mentioned supernatant is added, is placed in oscillation
2min is vibrated on device, then magnetic graphene is gathered into centrifugation bottom of the tube with magnet, supernatant is transferred in 10mL centrifuge tube, nitrogen
Air-blowing is dry, and mobile phase is settled to 1mL, crosses 0.22 μm of filter membrane, then carries out HPLC-MS/MS measurement analysis；
The veterinary drug is one or more of amantadine or trichomonas net；
The condition of the HPLC-MS/MS measurement analysis are as follows:
Chromatographic column: ZORBAX Eclipse Plus C18,1.8 μm, 3.0 × 100mm；Column temperature: 40 DEG C；Sample volume: 20 μ L；Stream
Dynamic phase: the aqueous formic acid that A volume fraction is 0.1%, B acetonitrile；HPLC gradient elution condition are as follows:
Ion source: electric spray ion source；Scanning mode: cation scanning；Detection mode: multiple reaction monitoring；Ion source temperature:
350℃；Gas flow rate: 10L/min；Nebulizer pressure: 40psi；
The mass spectrometry parameters of the veterinary drug:
The meat products is one kind of chicken or pork.
2. according to the method described in claim 1, it is characterized by: anhydrous magnesium sulfate described in step (3) and sodium chloride are equal
It is added in solid form.
3. according to the method described in claim 1, it is characterized by: anhydrous magnesium sulfate described in step (4) is with solid shape
What formula was added.
4. according to the method described in claim 1, it is characterized by: the revolving speed of homogenizer described in step (3) be 10000 turns/
min。
5. according to the method described in claim 1, it is characterized by: mobile phase described in step (4) is that acetonitrile/formic acid is water-soluble
Liquid, 20%V/80%V, wherein the volume fraction of formic acid is 0.1% in aqueous formic acid.
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| CN107300598B (en) * | 2017-08-22 | 2019-09-20 | 福建出入境检验检疫局检验检疫技术中心 | A kind of pre-treating method for Multiple Pesticides residue detection in tealeaves |
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| CN111426765B (en) * | 2020-04-17 | 2020-11-10 | 绿城农科检测技术有限公司 | Method for detecting macrolide antibiotics in honey and sample treatment method thereof |
| CN111650320B (en) * | 2020-07-03 | 2022-11-04 | 中国检验检疫科学研究院 | Detection method and kit for quinolone veterinary drugs based on magnetic solid-phase extraction |
| CN114324643B (en) * | 2021-12-24 | 2023-07-04 | 浙江树人学院（浙江树人大学） | Method for detecting macrolide antibiotics in organic fertilizer and sample treatment method thereof |
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