CN107664671B - Method for detecting residual medicine of animal-derived food - Google Patents
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Abstract
The invention discloses a method for detecting residual drugs of animal-derived food, which comprises the steps of pretreating a sample by QuEChERS, and then carrying out chromatography-mass spectrometry combined detection; the method for treating the sample by QuEChERS comprises the following steps: weighing a sample, placing the sample in a centrifuge tube, adding ethyl acetate, carrying out vortex mixing and centrifugation, transferring an organic layer into another centrifuge tube, then adding one piece of uniform proton of ethyl acetate and ceramic, manually oscillating and centrifuging, combining two times of supernate, carrying out nitrogen blowing concentration at constant temperature till the mixture is nearly dry, adding acetonitrile for redissolving, carrying out vortex mixing, adding a QuEChERS purifying agent, carrying out vortex mixing, filtering, and waiting for on-machine determination. The method has the characteristics of simple useful operation, short time consumption, high sensitivity and good reproducibility, and is suitable for large-scale application.
Description
Technical Field
The invention relates to the field of detection, in particular to detection of animal-derived food by QuEChERS-high performance liquid chromatography-tandem mass spectrometry.
Background
The hormones mainly comprise estrogen (Estrogens), androgen (Androgens), progestogen (Progestogens), glucocorticoid (Glucocorticoids) and the like, and are endocrine disrupting drugs with biological activity. Since the hormone medicine has the functions of improving the feed conversion rate and promoting the growth, the cultivation efficiency can be improved and the economic growth can be promoted, and the hormone medicine is illegally abused in the animal husbandry cultivation for decades. The way in which hormonal drugs are used in an irregular or excessive manner is the main route leading to residues of hormonal drugs in foods of animal origin. There is a lot of evidence that residual hormone drugs in animal-derived food have potential toxicity and carcinogenic hazard to human health, and for example, breast cancer, uterine cancer, prostate cancer and the like are probably caused by hormone drugs. Europe and many other countries therefore restrict and prohibit the illegal use of these hormonal drugs. The 176 bulletin of the Ministry of agriculture in China clearly stipulates that ten hormone medicaments such as diethylstilbestrol, estradiol and the like including estrogen, androgen, progestogen and anabolic hormone are prohibited from being added into feed and animal drinking water. The 235 publication states that nine hormones, such as diethylstilbestrol, megestrol acetate, and methyltestosterone, are prohibited from being detected in animal food. For three hormones, namely, fluoprogesterone acetate, dexamethasone and betamethasone, China makes the Maximum Residual Limit (MRL) regulation on the fluoprogesterone acetate, the dexamethasone and the betamethasone. The livestock meat is a main meat food source for people in China, and if the food containing hormone drug residues is sold on the market, the livestock meat has great harm to the mind and body of the people. Therefore, a monitoring and analyzing method for multi-residue hormone drugs in animal-derived food with high sensitivity and high reliability is needed to be developed.
The detection methods of hormone drug residues are numerous, and mainly include liquid chromatography (HPLC), gas chromatography-mass spectrometry (GC-MS), liquid chromatography-tandem mass spectrometry (LC-MS/MS) and the like. The LC-MS/MS has the advantages of simple and convenient pretreatment process, high sensitivity, no need of deriving a target substance and the like, thereby being widely applied to food safety detection. In the existing detection methods, the application of LC-MS/MS to detect certain class or several classes of hormone drugs has been reported. However, the reported detection method has strong pertinence of the sample pretreatment step, so that the application range of the detection method is single. Therefore, the establishment of a universal sample pretreatment method with simple operation, short time consumption, high sensitivity and good reproducibility has great significance for food safety detection.
Disclosure of Invention
The invention aims to disclose a method for simultaneously measuring 63 residual hormone drugs in animal-derived food.
The technical scheme adopted by the invention is as follows: a method for detecting residual drugs of animal-derived food comprises the steps of adopting a QuEChERS pretreatment sample, and then carrying out chromatography-mass spectrometry combined detection.
Preferably, the method for treating the sample by QuEChERS is as follows: weighing a sample, placing the sample in a centrifuge tube, adding ethyl acetate, carrying out vortex mixing and centrifugation, transferring an organic layer into another centrifuge tube, then adding one piece of uniform proton of ethyl acetate and ceramic, manually oscillating and centrifuging, combining two times of supernate, carrying out nitrogen blowing concentration at constant temperature till the mixture is nearly dry, adding acetonitrile for redissolving, carrying out vortex mixing, adding a QuEChERS purifying agent, carrying out vortex mixing, filtering, and waiting for on-machine determination.
Preferably, the QuEChERS scavenger is prepared from PSA, C18, MgSO4And (4) forming.
Further preferably, the QuEChERS purifying agent is prepared from PSA 20-80mg, C18 10-50mg, and MgSO4The dosage is 25-100 mg.
The residual medicine detected by the method is trenbolone, meperidinone, nandrolone, testosterone, mesterone, progesterone, 17-alpha-hydroxyprogesterone, 21-alpha-hydroxyprogesterone, fluoxymesterone, prednisolone, hydrocortisone, deoxycorticosterone acetate, fluorometholone, dexamethasone, prednisolone acetate, beclomethasone, dexamethasone acetate, fluticasone propionate, betamethasone propionate, bodhIDone, merolone, levonorgestrel, megestrol, prednisone, hydroxyprogesterone acetate, methylprednisolone, cortisone acetate, hydrocortisone acetate, chlormadinone acetate, fluocinolone acetate, flurandrenolone acetate, fludroxydroxydol, betamethasone valerate, megestrol acetate, methyltestosterone, alclomethasone propionate, danazol, altrenogest, dydrogesterone, medrogesterone acetate, Methylprednisolone acetate, clobetasone butyrate, diflorasone diacetate, mifepristone, betamethasone acetate, prednisone ester, amcinonide, beclomethasone dipropionate, estrone, norethindrone, cortisone, budesonide, clobetasol propionate, fludrocortisone acetate, hydrocortisone butyrate, triamcinolone acetonide acetate, deflazacort, halcinonide, flumethasone, hydrocortisone valerate, triamcinolone diacetate, fluocinolone acetonide acetate.
Preferably, the chromatographic detection conditions are reversed phase C18 chromatographic column with specification of 150mm × 2.1mm, sub-three micron chromatographic column.
Preferably, the chromatographic detection column temperature is 20-40 ℃, and the flow rate: 0.2-0.3mL/min, and the sample amount is 1-10 μ L.
Preferably, the mobile phase A of the chromatographic detection is 0.1-0.5% of formic acid water, the mobile phase B is acetonitrile, and the gradient elution procedure is as follows: 0-0.5min, 5% B, 0.5-0.51min, 30% B, 0.51-8min, 95% B, 8-10min, 95% B, 10-15min, 5% B.
The invention has the beneficial effects that: has the characteristics of simple useful operation, short time consumption, high sensitivity and good reproducibility, and is suitable for large-scale application.
Drawings
FIG. 1 shows the effect of different extraction solvents.
FIG. 2 shows the extraction results of different purification packing.
FIG. 3 shows the effect of extraction with different amounts of purification fillers.
Detailed Description
Examples
1. Preparation of Standard solutions
Trenbolone, meperidinone, nandrolone, testosterone, mesterone, progesterone, 17-alpha-hydroxyprogesterone, 21-alpha-hydroxyprogesterone, fluoxymesterone, prednisolone, hydrocortisone, deoxycorticosterone acetate, fluoromethalone, dexamethasone, prednisone acetate, prednisolone acetate, beclomethasone, dexamethasone acetate, fluticasone propionate, betamethasone propionate, bodiferone, megestrol, levonorgestrel, megestrol, prednisone, hydroxyprogesterone acetate, methylprednisolone, cortisone acetate, hydrocortisone acetate, chlormadinone acetate, fluocinolone acetate, flurandrenolone valerate, megestrol acetate, metdrosterone, meclotestosterone, alclomethasone propionate, danazol, etc. are available from dr. Altrenogest, dydrogesterone, medrenone acetate, methylprednisolone acetate, clobetasone butyrate, diflorasone diacetate, mifepristone, betamethasone acetate, prednisone acetate, amcinonide, beclomethasone dipropionate, etc. are available from Beijing TRC. Estrone, norethindrone, cortisone, budesonide, clobetasol propionate, and the like were purchased from the institute of food and drug testing, china. Fludrocortisone acetate, hydrocortisone butyrate, triamcinolone acetonide acetate, deflazacort, halcinonide, flumethasone, hydrocortisone valerate, triamcinolone diacetate, fluocinolone acetonide acetate, and the like are available from Shanghai' an spectral Co.
Accurately weighing the 63 hormone drug reference substances, preparing standard stock solutions with the mass concentration of 1mg/mL by using methanol respectively, and storing in a refrigerator at the temperature of-18 ℃. The stock solution is prepared into a mixed standard working solution with the concentration of 1 mu g/mL by using methanol, and the mixed standard working solution is stored in a refrigerator at 4 ℃ and prepared into standard working solutions with different concentrations when needed.
2. Sample pretreatment
Accurately weighing 5.0g (accurate to 0.01g) of homogenized meat sample, placing in 50mL polypropylene centrifuge tube with screw cap, adding 10mL ethyl acetate, mixing for 1min by vortex on a rapid mixer, centrifuging for 5min at 4000r/min, transferring the organic layer into another clean 50mL polypropylene centrifuge tube with screw cap, adding 10mL ethyl acetate and ceramic homogeneous proton, manually oscillating for 30s, centrifuging for 5min at 4000r/min, mixing the two supernatants, concentrating at 45 deg.C under constant temperature with nitrogen blowing to near dry, adding 2mL acetonitrile for redissolving, mixing for 1min by vortex, adding QuEChERS purifying agent (20-80mg PSA, 10-50mg C18, 25-100mg MgSO 4) to obtain a mixture4) Vortex and mix evenly for 1min, filter membrane of 0.22 μm, wait for machine to determine.
3. Preparation of matrix matching mixed standard solution
Taking a blank matrix sample, processing the sample according to the method 1 to obtain blank extracting solutions, respectively adding appropriate amounts of standard working solutions, and preparing into 8 mixed matrix standard solutions with different concentrations (0.2 mu g/L, 0.5 mu g/L, 1 mu g/L, 2 mu g/L, 5 mu g/L, 10 mu g/L, 15 mu g/L and 20 mu g/L) for use.
4. Chromatographic and mass spectral conditions
A chromatographic column: c18 chromatography column (150mm x 2.1mm, sub-three micron), column temperature 20-40 ℃, flow rate: 0.2-0.3mL/min, and the sample amount is 1-10 μ L. Mobile phase a was 0.1% formic acid water, B was acetonitrile, gradient elution procedure: 0-0.5min, 5% B, 0.5-0.51min, 30% B, 0.51-8min, 95% B, 8-10min, 95% B, 10-15min, 5% B.
Electrospray ion source (ESI); the acquisition mode is a preset multi-reaction detection mode (sMRM); ESI + spray voltage is 5500V, and mass spectrum parameters such as a monitored ion pair (Q1/Q3), Declustering Potential (DP), Collision Energy (CE) and collision cell exit voltage (CXP) of each analyte are shown in Table 1.
Table 163 major mass spectral parameters and retention times of the hormones
5 optimization of Mass Spectrometry and chromatography conditions
According to the ionization property of 63 hormone drugs, a syringe pump is adopted for continuous sample injection, and the mixed standard solution of 0.05 mu g/mL is subjected to mother ion full scanning in a positive ion mode to determine the excimer ions of the hormone drugs. And then, carrying out full scanning on the sub-ions of each quasi-molecular ion to determine that the ion abundance is high, and two pairs of sub-ions with smaller interference are qualitative ions, wherein the ion abundance is quantitative ions. And then, optimizing the collision energy, the outlet voltage and the declustering voltage to enable the response value of the two pairs of daughter ions to reach the maximum.
The flow ratio was compared with a formic acid water (formic acid content 0.1% v/v) -methanol system and a formic acid water (formic acid content 0.1% v/v) -acetonitrile system. The result shows that the separation degree, the peak response strength and the matrix interference condition of the organic phase obtained by adopting the acetonitrile system are all superior to those of the methanol system, and finally, the acetonitrile is determined to be adopted as the organic phase mobile phase.
Compared with the traditional MRM mode, the preset multi-reaction monitoring (sMRM) mode is adopted, so that high sensitivity is kept, and meanwhile, multiple hormone drugs can be detected in parallel at different time periods, the detection flux of the object to be detected is greatly improved, and confusion caused by the fact that the compound has the same parent ions and daughter ions when ion pairs are extracted can be avoided.
Optimization of QuEChERS pretreatment conditions
The hormone medicine usually adopts methanol and acetonitrile as extraction solvents. Methanol, acetonitrile, ethyl acetate and mixed solvents ethyl acetate of different proportions are adopted in the experiment: acetonitrile (volume ratio of 4:1 and 1:1), ethyl acetate: methanol (4: 1 and 1:1 by volume) was used for comparative experiments. The results show that: the extraction efficiency of methanol on various hormones is low, and the extraction rate of acetonitrile is improved compared with that of methanol, but the extraction rate of acetonitrile is not as high as that of ethyl acetate. The extraction rate of the four mixed solvents is increased along with the increase of the proportion of the ethyl acetate. Most hormone drugs are weak polarity, ethyl acetate is a weak polarity solvent, the ethyl acetate extraction rate is highest according to the principle of similarity and compatibility, but the ethyl acetate adopted as the extraction solvent has the defects that protein cannot be purified simultaneously, and extracted grease is more than other solvents, so that the difficulty is increased for the next QuEChERS purification step. FIG. 1 shows a comparison of the recovery of 63 analytes for each solvent.
The animal-derived food has complex matrix and is rich in nutritional ingredients such as protein, oil, carbohydrate and various minerals. Impurities adsorbed by different purifying fillers in the QuEChERS filler are different, polar fatty acid and sterol compounds in the PSA main adsorption matrix, C18 can remove impurities such as fat, saccharides and the like, and GBC has strong affinity to a planar structure compound and can effectively remove impurities such as pigments and the like. In the experiment, firstly, the adsorption effect of each filler on the substances to be detected when the filler is used independently is compared, and the result shows that C18 has no obvious adsorption effect on the hormone medicines, PSA has a slight adsorption effect on the target hormone medicines, and GBC has a serious adsorption effect on the hormone medicines, so that the purifying filler is not selected from GBC, and the purifying filler is shown in figure 2.
For optimal purification, the preferred method is used to separate PSA, C18 and MgSO4The amount of (c) is screened. First, C18 was determined to be 25mg, MgSO4At 50mg, the amount of PSA is selected, and when the amount of PSA is too small, the recovery is generally low, possibly incomplete purging leading to a higher ion suppression effect, whereas when the amount of PSA is increased to 80mg, the percent recovery decreases, demonstrating that the purging charge has begun to adsorb a large amount of the target, and therefore the optimum amount of PSA is designated 20-80 mg. Finally, the optimal QuEChERS purification filler is determined to be PSA dosage of 20-80mg, C18 dosage of 10-50mg and MgSO4The dosage is 25-100 mg. The best purifying solvent acetonitrile of QuEChERS is selected as constant volume liquid, and the functions of concentration and protein removal are achieved during purification. The clean-up packing screen is shown in FIG. 3.
7. Linear relationship with detection and quantitation limits
And (4) taking the peak area of the component to be measured as the ordinate and the mass concentration as the abscissa, and drawing a standard curve. The limit of detection (LOD) and limit of quantitation (LOQ) of the analyte were determined as the signal-to-noise ratio (S/N ═ 3) and (S/N ═ 10). The equation of the working curve, the correlation coefficient and the linear range are shown in table 2. The detection and quantification limits are shown in Table 3. As can be seen from Table 2, the 63 hormonal drugs showed good linear relationship in the linear range, and the correlation coefficient of each analyte was greater than 0.99. As shown in Table 3, the LOD ranges of the 63 hormonal drugs are 0.01 to 0.3 μ g/Kg, and the LOQ ranges from 0.03 to 1 μ g/Kg.
Linear curve equation, correlation coefficient and linear range of 263 hormone drugs
TABLE 3.63 detection limits and lower quantitation limits for hormones
8. Recovery experiments and reproducibility
Taking 5g of negative chicken, pork and fish samples, respectively adding mixed standard solutions with the levels of 1 mu g/kg, 5 mu g/kg and 10 mu g/kg, wherein the standard addition levels of dexamethasone are 0.5 mu g/kg, 0.75 mu g/kg and 1 mu g/kg, carrying out 6 recovery experiments, and the results of the recovery rate and the precision after detection are listed in tables 4 and 5. The results show that the recovery rate is between 61.38 and 119.25 percent, the relative standard deviation is between 0.5 and 15.7 percent, and the method has better precision and can meet the detection requirement of actual samples.
Table 463 results of recovery test of hormone drugs
Precision test results for Table 563 hormone drugs
The data show that the method can simultaneously identify multiple residual hormone drugs, is simple and convenient to operate, has high accuracy and is suitable for large-scale application.
Claims (4)
1. A method for detecting residual drugs of animal-derived food comprises the steps of adopting a QuEChERS pretreatment sample, and then carrying out chromatography-mass spectrometry combined detection;
the method for pretreating the sample by the QuEChERS comprises the following steps: weighing a sample, placing the sample in a centrifuge tube, adding ethyl acetate, carrying out vortex mixing and centrifugation, transferring an organic layer into another centrifuge tube, then adding one piece of ethyl acetate and ceramic uniform protons, manually oscillating and centrifuging, combining two supernatants, carrying out nitrogen blowing concentration at constant temperature till the supernatant is nearly dry, adding acetonitrile for redissolving, carrying out vortex mixing, adding a QuEChERS purifying agent, carrying out vortex mixing, carrying out a filter membrane, and waiting for on-machine determination;
the QuEChERS purifying agent is prepared from PSA 20-80mg, C18 10-50mg, and MgSO425-100 mg;
the residual medicine is trenbolone, meperidone, nandrolone, testosterone, mesterolone, progesterone, 17-alpha-hydroxyprogesterone, 21-alpha-hydroxyprogesterone, fluoxymesterone, prednisolone, hydrocortisone, deoxycorticosterone acetate, fluorometholone, dexamethasone, prednisolone acetate, beclomethasone, dexamethasone acetate, fluticasone propionate, betamethasone propionate, bodhledione, megestrol, levonorgestrel, megestrol, prednisone, hydroxyprogesterone acetate, methylprednisolone, cortisone acetate, hydrocortisone acetate, chlormadinone acetate, fluocinolone acetate, flurandrenolone, fludroxysone, betamethasone valerate, megestrol acetate, megestrol, meclomethasone propionate, danazol, pregnenol, dydrogesterone, medrogesterone acetate, Methylprednisolone acetate, clobetasone butyrate, diflorasone diacetate, mifepristone, betamethasone acetate, prednisone ester, amcinonide, beclomethasone dipropionate, estrone, norethindrone, cortisone, budesonide, clobetasol propionate, fludrocortisone acetate, hydrocortisone butyrate, triamcinolone acetonide acetate, deflazacort, halcinonide, flumethasone, hydrocortisone valerate, triamcinolone diacetate, and fluocinolone acetonide acetate;
the chromatographic column adopted by the chromatographic detection condition is a reversed phase C18 chromatographic column; the mobile phase A is 0.1-0.5% formic acid water, the B is acetonitrile, the gradient elution procedure: 0-0.5min, 5% B, 0.5-0.51min, 30% B, 0.51-8min, 95% B, 8-10min, 95% B, 10-15min, 5% B;
the acquisition mode of the mass spectrometry detection is a preset multi-reaction detection mode; the electrospray ion source + spray voltage is 5500V, and parameters of the monitored ion pairs, the cluster removing voltage, the collision energy and the outlet voltage of the collision chamber of each object to be detected are as follows:
2. the detection method according to claim 1, wherein the reverse phase C18 chromatographic column has a specification of 150mm x 2.1mm, sub-three micron chromatographic column.
3. The detection method according to claim 1, wherein the temperature of the chromatographic detection column is 20-40 ℃, and the flow rate: 0.2-0.3mL/min, and the sample amount is 1-10 μ L.
4. The detection method according to claim 1, wherein the animal-derived food is chicken, pork, or fish.
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| CN111595956B (en) * | 2020-04-23 | 2021-07-13 | 浙江大学 | Method for detecting hormone and neurotransmitter in serum |
| CN113588828B (en) * | 2021-07-30 | 2023-06-23 | 西安市食品药品检验所(西安市药品不良反应监测中心) | Method for simultaneously detecting forty-eight stimulants in animal-derived food |
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