CN109884217B - High-throughput analysis method for chemical residual substances in food - Google Patents
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Abstract
The application discloses a high-throughput analysis method for chemical residual substances in food, which comprises the following steps: sample pretreatment, preparation of a standard working solution and UPLC-MS/MS measurement, wherein the sample pretreatment comprises the following steps: crushing and drying, namely taking animal-derived food, concentrating if the food is liquid, and crushing and drying if the food is solid; until the water content is lower than 2%, pulverizing and sieving; secondly, extracting, namely adding a certain amount of water, potassium chloride and nicotinamide into a sample, stirring and reacting for 5-10 min at 55-60 ℃, and filtering to obtain filtrate; mixing the filtrate and chitosan according to a mass ratio of 1: 0.3-0.4, stirring and reacting at 45-50 ℃ for 5-10 min, filtering, concentrating the filtrate at 40-50 ℃ until the water content is lower than 1% to obtain a solid to be detected, dissolving the solid to be detected with an initial mobile phase, and using the solid to be detected for UPLC-MS/MS determination.
Description
Technical Field
The invention relates to a high-throughput analysis method for chemical residual substances in food.
Background
With the development of social industrialization, environmental pathogenic factors, such as atmospheric pollution, water pollution and food pollution, have increasingly remarkable influence on health. Chemical contamination of food products has been an environmental pathogenic factor that has received considerable attention. At present, more than 500 thousands of known exogenous chemical substances are available, and at least 6 thousands of the known exogenous chemical substances enter the production and life of people, such as various industrial raw materials and products, medicines, pesticides, cosmetics, biotoxins and the like. These chemicals can enter the food product as contaminants through the raw material production, processing, cooking, packaging, storage and transportation of the food product. Food contaminants include substances used in food production and environmental chemical or biological contaminants introduced elsewhere in the food market, such as pesticides, veterinary drugs, mycotoxins, industrial contaminants, and the like.
Veterinary drugs play an important role in preventing and treating animal diseases, improving productivity and improving the quality of animal products. However, the phenomenon of veterinary drug abuse is ubiquitous in the current animal husbandry due to the lack of scientific knowledge and the economic pursuit of the producer. With the shift of demand type to quality type of animal-derived food, veterinary drug residues in animal-derived food have gradually become a focus of worldwide attention. The veterinary drug residue refers to prototype drug or metabolite thereof accumulated or retained in livestock and fowl organism or product (such as egg, milk, meat, etc.), including impurity residue related to veterinary drug. Abuse of veterinary drugs easily causes residues of harmful substances in animal-derived foods, which causes direct harm to human health. An important means for monitoring veterinary drug residues in animal derived foods is to establish a rapid and accurate residue analysis method.
Chinese patent with publication date of 2017, 7 and 28 and publication number of CN106990195A discloses a method for detecting veterinary drug residues of sulfonamides and quinolones in animal-derived food, which comprises (1) preparation of standard solution; (2) pretreating a sample; (3) liquid-mass separation detection; the veterinary drug residue is detected by extracting 1% formic acid acetonitrile, degreasing normal hexane and combining high-resolution mass spectrometry.
Researches show that the water solubility of the sulfonamides veterinary drug is low, the quinolones veterinary drug has certain solubility in water but also has certain solubility in an organic solvent, so that when the sample pretreatment method in the prior art is adopted, the extraction rate of the sulfonamides veterinary drug is reduced to a certain extent when 1% formic acid acetonitrile is extracted, and the sulfonamides veterinary drug and the quinolones veterinary drug have certain loss when n-hexane is degreased. In the prior art, a certain improvement space still exists for the extraction of sulfonamide and quinolone veterinary drugs, the accuracy of content determination can be improved by improving the extraction rate, the detection amount of an analysis sample is reduced, and the method has important value.
Disclosure of Invention
The invention aims to provide a high-throughput analysis method for chemical residual substances in food, which has the advantage of improving the extraction rate of veterinary drugs.
The technical purpose of the invention is realized by the following technical scheme:
a high-throughput analysis method for chemical residual substances in food comprises the steps of sample pretreatment, standard working solution preparation and UPLC-MS/MS measurement which are sequentially arranged, wherein the sample pretreatment comprises the following steps:
pulverizing and drying
Taking animal-derived food as a sample to be detected, concentrating the sample to be detected at 40-50 ℃ until the water content is lower than 2% if the sample to be detected is liquid, crushing and sieving the concentrated sample by a 50-100-mesh sieve; if the sample to be detected is solid, stirring and drying the sample at 40-50 ℃ until the water content is lower than 2%, and crushing and sieving the sample by a 50-100-mesh sieve;
extraction of
Taking a crushed and dried sample to be detected, adding water, potassium chloride and nicotinamide, stirring and reacting for 5-10 min at 55-60 ℃, filtering and taking a filtrate, wherein the mass ratio of the sample to be detected to the water, the potassium chloride and the nicotinamide is 1: 10-15: 0.2-0.3: 0.05-0.08; mixing the filtrate and chitosan according to a mass ratio of 1: 0.3-0.4, stirring and reacting at 45-50 ℃ for 5-10 min, filtering to obtain the filtrate, concentrating the filtrate at 40-50 ℃ until the water content is lower than 1% to obtain a solid to be detected, dissolving the solid to be detected by using an initial mobile phase, and using the solid to be detected for UPLC-MS/MS determination.
Preferably, the extraction step comprises the following steps:
taking a crushed and dried sample to be detected, adding water, potassium chloride and nicotinamide, stirring and reacting for 5-10 min at 55-60 ℃, adding a metal organic framework material UIO-66, nano titanium dioxide and polyethylene glycol 2000, stirring and dispersing for 5-10 min, filtering and taking a filtrate, wherein the mass ratio of the sample to be detected, the water, the potassium chloride, the nicotinamide, the metal organic framework material UIO-66, the nano titanium dioxide and the polyethylene glycol 2000 is 1: 10-15: 0.2-0.3: 0.05-0.08: 0.01-0.02; mixing the filtrate and chitosan according to a mass ratio of 1: 0.3-0.4, stirring and reacting at 45-50 ℃ for 5-10 min, filtering to obtain the filtrate, concentrating the filtrate at 40-50 ℃ until the water content is lower than 1% to obtain a solid to be detected, dissolving the solid to be detected by using an initial mobile phase, and using the solid to be detected for UPLC-MS/MS determination.
Preferably, the standard working solution formulation comprises the steps of: accurately weighing all target veterinary drug standard products, preparing 1000mg/l standard stock solution by using initial mobile phase, diluting the standard stock solution to 5 concentration points by using the initial mobile phase, and taking the 5 concentration points as standard working solution; the target veterinary drug is selected from sulfonamides and/or quinolones;
the conditions for the UPLC-MS/MS assay were as follows:
chromatographic conditions are as follows: waters Acquity UPLC BEH C18A chromatographic column, wherein a mobile phase A is methanol, a mobile phase B is 1wt% formic acid aqueous solution, and the elution mode is gradient elution; the gradient elution procedure was, by volume: 0-2.0 min10% of mobile phase A +90% of 1wt% of formic acid aqueous solution, 2.1-8.0 min30% of mobile phase A +70% of 1wt% of formic acid aqueous solution, 8.1-14.0 min90% of mobile phase A +10% of 1wt% of formic acid aqueous solution, and 14.1-16.0 min10% of mobile phase A +90% of 1wt% of formic acid aqueous solution;
mass spectrum conditions: electrospray ionization (ESI +) ion source with a temperature source of 110 deg.C, a desolvation temperature of 350 deg.C, and a desolvation gas flow rate of 600 L.h-1The temperature of the reverse blowing air flow of the taper hole is 50 L.h-1The mass spectrum scanning method is a multi-reaction detection scanning method with multiple time periods.
Preferably, the method comprises the following steps:
(1) sample pretreatment
Pulverizing and drying
Taking animal-derived food as a sample to be detected, concentrating the sample to be detected at 40-50 ℃ until the water content is lower than 2% if the sample to be detected is liquid, crushing and sieving the concentrated sample by a 50-100-mesh sieve; if the sample to be detected is solid, stirring and drying the sample at 40-50 ℃ until the water content is lower than 2%, and crushing and sieving the sample by a 50-100-mesh sieve;
extraction of
Taking a crushed and dried sample to be detected, adding water, potassium chloride and nicotinamide, stirring and reacting for 5-10 min at 55-60 ℃, filtering and taking a filtrate, wherein the mass ratio of the sample to be detected to the water, the potassium chloride and the nicotinamide is 1: 10-15: 0.2-0.3: 0.05-0.08; mixing the filtrate with chitosan according to a mass ratio of 1: 0.3-0.4, stirring and reacting at 45-50 ℃ for 5-10 min, filtering to obtain the filtrate, concentrating the filtrate at 40-50 ℃ until the water content is lower than 1% to obtain a solid to be detected, dissolving the solid to be detected with an initial mobile phase, and using the solid to be detected for UPLC-MS/MS determination;
(2) standard working solution preparation
Accurately weighing all target veterinary drug standard products, preparing 1000mg/l standard stock solution by using initial mobile phase, diluting the standard stock solution to 5 concentration points by using the initial mobile phase, and taking the 5 concentration points as standard working solution; the target veterinary drug is selected from sulfonamides and/or quinolones;
(3) UPLC-MS/MS assay
The measurement was carried out as follows:
chromatographic conditions are as follows: waters Acquity UPLC BEH C18A chromatographic column, wherein a mobile phase A is methanol, a mobile phase B is 1wt% formic acid aqueous solution, and the elution mode is gradient elution; the gradient elution procedure was, by volume: 0-2.0 min10% of mobile phase A +90% of 1wt% of formic acid aqueous solution, 2.1-8.0 min30% of mobile phase A +70% of 1wt% of formic acid aqueous solution, 8.1-14.0 min90% of mobile phase A +10% of 1wt% of formic acid aqueous solution, and 14.1-16.0 min10% of mobile phase A +90% of 1wt% of formic acid aqueous solution;
mass spectrum conditions: electrospray ionization (ESI +) ion source with a temperature source of 110 deg.C, a desolvation temperature of 350 deg.C, and a desolvation gas flow rate of 600 L.h-1The temperature of the reverse blowing air flow of the taper hole is 50 L.h-1The mass spectrum scanning method is a multi-reaction detection scanning method with multiple time periods.
Preferably, the method comprises the following steps:
(1) sample pretreatment
Pulverizing and drying
Taking animal-derived food as a sample to be detected, concentrating the sample to be detected at 40-50 ℃ until the water content is lower than 2% if the sample to be detected is liquid, crushing and sieving the concentrated sample by a 50-100-mesh sieve; if the sample to be detected is solid, stirring and drying the sample at 40-50 ℃ until the water content is lower than 2%, and crushing and sieving the sample by a 50-100-mesh sieve;
extraction of
Taking a crushed and dried sample to be detected, adding water, potassium chloride and nicotinamide, stirring and reacting for 5-10 min at 55-60 ℃, adding a metal organic framework material UIO-66, nano titanium dioxide and polyethylene glycol 2000, stirring and dispersing for 5-10 min, filtering and taking a filtrate, wherein the mass ratio of the sample to be detected, the water, the potassium chloride, the nicotinamide, the metal organic framework material UIO-66, the nano titanium dioxide and the polyethylene glycol 2000 is 1: 10-15: 0.2-0.3: 0.05-0.08: 0.01-0.02; mixing the filtrate with chitosan according to a mass ratio of 1: 0.3-0.4, stirring and reacting at 45-50 ℃ for 5-10 min, filtering to obtain the filtrate, concentrating the filtrate at 40-50 ℃ until the water content is lower than 1% to obtain a solid to be detected, dissolving the solid to be detected with an initial mobile phase, and using the solid to be detected for UPLC-MS/MS determination;
(2) standard working solution preparation
Accurately weighing all target veterinary drug standard products, preparing 1000mg/l standard stock solution by using initial mobile phase, diluting the standard stock solution to 5 concentration points by using the initial mobile phase, and taking the 5 concentration points as standard working solution; the target veterinary drug is selected from sulfonamides and/or quinolones;
(3) UPLC-MS/MS assay
The measurement was carried out as follows:
chromatographic conditions are as follows: waters Acquity UPLC BEH C18A chromatographic column, wherein a mobile phase A is methanol, a mobile phase B is 1wt% formic acid aqueous solution, and the elution mode is gradient elution; the gradient elution procedure was, by volume: 0-2.0 min10% of mobile phase A +90% of 1wt% of formic acid aqueous solution, 2.1-8.0 min30% of mobile phase A +70% of 1wt% of formic acid aqueous solution, 8.1-14.0 min90% of mobile phase A +10% of 1wt% of formic acid aqueous solution, and 14.1-16.0 min10% of mobile phase A +90% of 1wt% of formic acid aqueous solution;
mass spectrum conditions: electrospray ionization (ESI +) ion source with a temperature source of 110 deg.C, a desolvation temperature of 350 deg.C, and a desolvation gas flow rate of 600 L.h-1The temperature of the reverse blowing air flow of the taper hole is 50 L.h-1The mass spectrum scanning method is a multi-reaction detection scanning method with multiple time periods.
The technical effects of the invention are mainly reflected in the following aspects:
in a water environment of 55-60 ℃, quinolone veterinary drugs in the crushed animal-derived food are dissolved in water, sulfonamide veterinary drugs react with nicotinamide in the water at the temperature to obtain nicotinamide eutectic of the sulfonamide veterinary drugs, potassium chloride is used as an ion concentration regulator when the eutectic is generated by the reaction, the solubility of the eutectic in the water is high, the property that the sulfonamide veterinary drugs are insoluble in the water is changed, and because grease and the like in the animal-derived food are insoluble in the water, a filtrate concentrate I obtained after extraction in the water environment is impurities such as sulfonamide eutectic of sulfonamide veterinary drugs, quinolone veterinary drugs and a very small amount of grease with good water solubility, and the water solubility and no other solvents participate, the extraction rate of the sulfonamide veterinary drugs and the quinolone veterinary drugs is obviously increased, and the extraction process is environment-friendly and safe; then, the filtrate concentrate I acts on the chitosan, the sulfonamide veterinary drug in the sulfonamide veterinary drug nicotinamide eutectic is replaced by the chitosan, the dissociated sulfonamide veterinary drug can still keep better solubility in the chitosan and chitosan nicotinamide eutectic aqueous solution, and the dissociated product is measured to obtain better detection effect; in addition, the metal organic framework material UIO-66, the nano titanium dioxide and the polyethylene glycol 2000 are added in the extraction step, so that impurities such as grease and the like in the metal organic framework material can be selectively adsorbed and coated to form a solid, the difficulty of emulsion-like or oily substances in the filtering step and the apparent judgment of the reaction process in the treatment process are reduced, the coating of the impurities such as the grease and the like on veterinary drugs can be reduced after the substances are added, and the extraction rate of the veterinary drugs is further improved; is suitable for low content detection and has important significance for high-throughput analysis.
Drawings
FIG. 1 is an XRD diagram of a sulfamethazine nicotinamide eutectic crystal (the molar ratio is 1: 1);
FIG. 2 is an XRD pattern of sulfathiazole nicotinamide eutectic (molar ratio is 1: 1);
fig. 3 is an XRD pattern of sulfaquinoxaline nicotinamide eutectic (molar ratio 1: 1).
Detailed Description
The following detailed description of the embodiments of the present invention is provided in order to make the technical solution of the present invention easier to understand and understand.
Example 1: a high-throughput analysis method for chemical residual substances in food comprises the following steps:
(1) sample pretreatment
Pulverizing and drying
Taking animal-derived food as a sample to be detected, concentrating the sample at 45 ℃ until the water content is lower than 2% if the sample to be detected is liquid, crushing and sieving the concentrated sample with a 100-mesh sieve; if the sample to be detected is solid, stirring and drying at 45 ℃ until the water content is lower than 2%, crushing and sieving by a 100-mesh sieve;
extraction of
Taking a crushed and dried sample to be detected, adding water, potassium chloride and nicotinamide, stirring and reacting for 8min at 58 ℃, adding a metal organic framework material UIO-66, nano titanium dioxide and polyethylene glycol 2000, stirring and dispersing for 8min, filtering to obtain a filtrate, wherein the mass ratio of the sample to be detected, the water, the potassium chloride, the nicotinamide, the metal organic framework material UIO-66, the nano titanium dioxide and the polyethylene glycol 2000 is 1:12:0.24:0.06:0.014:0.015: 0.015; mixing the filtrate and chitosan according to a mass ratio of 1:0.33, stirring and reacting at 48 ℃ for 8min, filtering to obtain a filtrate, concentrating the filtrate at 45 ℃ until the water content is lower than 1% to obtain a solid to be detected, and dissolving the solid to be detected by using an initial mobile phase for UPLC-MS/MS determination;
(2) standard working solution preparation
Accurately weighing all target veterinary drug standard products, preparing 1000mg/l standard stock solution by using initial mobile phase, diluting the standard stock solution to 5 concentration points by using the initial mobile phase, and taking the 5 concentration points as standard working solution; the target veterinary drug is selected from sulfonamides and/or quinolones;
(3) UPLC-MS/MS assay
The measurement was carried out as follows:
chromatographic conditions are as follows: waters Acquity UPLC BEH C18A chromatographic column, wherein a mobile phase A is methanol, a mobile phase B is 1wt% formic acid aqueous solution, and the elution mode is gradient elution; the gradient elution procedure was, by volume: 0-2.0 min10% of mobile phase A +90% of 1wt% of formic acid aqueous solution, 2.1-8.0 min30% of mobile phase A +70% of 1wt% of formic acid aqueous solution, 8.1-14.0 min90% of mobile phase A +10% of 1wt% of formic acid aqueous solution, and 14.1-16.0 min10% of mobile phase A +90% of 1wt% of formic acid aqueous solution;
mass spectrum conditions: electrospray ionization (ESI +) ion source with a temperature source of 110 deg.C, a desolvation temperature of 350 deg.C, and a desolvation gas flow rate of 600 L.h-1Inverse taper holeThe blowing temperature is 50 L.h-1The mass spectrum scanning method is a multi-reaction detection scanning method with multiple time periods.
Example 2: a method for high throughput analysis of chemical residue in food, which is different from example 1 in that (1) sample pretreatment is replaced with the following method:
pulverizing and drying
Taking animal-derived food as a sample to be detected, concentrating the sample at 40 ℃ until the water content is lower than 2% if the sample to be detected is liquid, crushing and sieving the concentrated sample with a 50-mesh sieve; if the sample to be detected is solid, stirring and drying at 40 ℃ until the water content is lower than 2%, crushing and sieving by a 50-mesh sieve;
extraction of
Taking a crushed and dried sample to be detected, adding water, potassium chloride and nicotinamide, stirring and reacting for 10min at 55 ℃, adding a metal organic framework material UIO-66, nano titanium dioxide and polyethylene glycol 2000, stirring and dispersing for 10min, filtering to obtain a filtrate, wherein the mass ratio of the sample to be detected, the water, the potassium chloride, the nicotinamide, the metal organic framework material UIO-66, the nano titanium dioxide and the polyethylene glycol 2000 is 1:10:0.2:0.05:0.01:0.01: 0.01; mixing the filtrate and chitosan according to the mass ratio of 1:0.3, stirring and reacting at 45 ℃ for 10min, filtering to obtain the filtrate, concentrating the filtrate at 40 ℃ until the water content is lower than 1% to obtain a solid to be detected, and dissolving the solid to be detected by using an initial mobile phase for UPLC-MS/MS determination.
Example 3: a method for high throughput analysis of chemical residue in food, which is different from example 1 in that (1) sample pretreatment is replaced with the following method:
pulverizing and drying
Taking animal-derived food as a sample to be detected, concentrating the sample at 50 ℃ until the water content is lower than 2% if the sample to be detected is liquid, crushing and sieving the concentrated sample with a 100-mesh sieve; if the sample to be detected is solid, stirring and drying at 50 ℃ until the water content is lower than 2%, crushing and sieving by a 100-mesh sieve;
extraction of
Taking a crushed and dried sample to be detected, adding water, potassium chloride and nicotinamide, stirring and reacting for 5min at 60 ℃, adding a metal organic framework material UIO-66, nano titanium dioxide and polyethylene glycol 2000, stirring and dispersing for 5min, filtering to obtain a filtrate, wherein the mass ratio of the sample to be detected, the water, the potassium chloride, the nicotinamide, the metal organic framework material UIO-66, the nano titanium dioxide and the polyethylene glycol 2000 is 1:15:0.3:0.08:0.02:0.02: 0.02; mixing the filtrate and chitosan according to the mass ratio of 1:0.4, stirring and reacting at 50 ℃ for 5min, filtering to obtain the filtrate, concentrating the filtrate at 50 ℃ until the water content is lower than 1% to obtain a solid to be detected, and dissolving the solid to be detected by using an initial mobile phase for UPLC-MS/MS determination.
Example 4: a method for high throughput analysis of chemical residue in food, which is different from example 1 in that (1) the extraction step of sample pretreatment is replaced by the following method:
taking a crushed and dried sample to be detected, adding water, potassium chloride and nicotinamide, stirring and reacting for 8min at 58 ℃, filtering and taking filtrate, wherein the mass ratio of the sample to be detected to the water, the potassium chloride and the nicotinamide is 1:12:0.24: 0.06; mixing the filtrate and chitosan according to the mass ratio of 1:0.33, stirring and reacting at 48 ℃ for 8min, filtering to obtain the filtrate, concentrating the filtrate at 45 ℃ until the water content is lower than 1% to obtain a solid to be detected, and dissolving the solid to be detected by using an initial mobile phase for UPLC-MS/MS determination.
Example 5: a method for analyzing chemical residue in food with high throughput is different from the method in example 1 in that (3) UPLC-MS/MS measurement is determined by the method in example 1 referring to CN 101358953B.
Comparative example 1: a method for high throughput analysis of chemical residue in food, which is different from example 1 in that (1) sample pretreatment is replaced with the following method:
referring to example 1 of CN103760269B, animal muscle tissue is crushed fully by a processor, frozen and preserved, 5.0g of unfrozen animal derived food is weighed accurately, placed in a 50ml centrifuge tube, 10.0ml of 10wt% trichloroacetic acid and acetonitrile extract (V: V =20: 80) is added, after fully homogenizing, ultrasonic extraction is carried out for 10min, 10000 r.min-1Centrifuging for 10min, transferring supernatant into another 50ml centrifuge tube, extracting residue with 10.0ml extractive solution once again, mixing extractive solutions, and blow drying the extractive solution at 30 deg.C under nitrogen. The initial mobile phase for the residue2.0ml of the mixture is dissolved and evenly mixed by vortex at 10000 r.min-1High speed centrifugation for 10 min. Taking a proper amount of supernatant, and filtering the supernatant by using a 0.45 mu m microporous filter membrane for UPLV-MS/MS determination.
Comparative example 2: a method for high throughput analysis of chemical residue in food, which is different from example 1 in that (1) sample pretreatment is replaced with the following method:
taking the crushed and dried sample to be detected, adding water and nicotinamide, stirring and reacting for 8min at 58 ℃, filtering and taking filtrate, wherein the mass ratio of the sample to be detected to the water to the nicotinamide is 1:12: 0.06; mixing the filtrate and chitosan according to the mass ratio of 1:0.33, stirring and reacting at 48 ℃ for 8min, filtering to obtain the filtrate, concentrating the filtrate at 45 ℃ until the water content is lower than 1% to obtain a solid to be detected, and dissolving the solid to be detected by using an initial mobile phase for UPLC-MS/MS determination.
Comparative example 3: a method for high throughput analysis of chemical residue in food, which is different from example 1 in that (1) sample pretreatment is replaced with the following method:
taking a crushed and dried sample to be detected, adding water and potassium chloride, stirring and reacting at 58 ℃ for 8min, filtering to obtain a filtrate, wherein the mass ratio of the sample to be detected to the water to the potassium chloride is 1:12: 0.24; mixing the filtrate and chitosan according to the mass ratio of 1:0.33, stirring and reacting at 48 ℃ for 8min, filtering to obtain the filtrate, concentrating the filtrate at 45 ℃ until the water content is lower than 1% to obtain a solid to be detected, and dissolving the solid to be detected by using an initial mobile phase for UPLC-MS/MS determination.
Comparative example 4: a method for high throughput analysis of chemical residue in food, which is different from example 1 in that (1) the extraction step of sample pretreatment is replaced by the following method:
taking a crushed and dried sample to be detected, adding water, potassium chloride and nicotinamide, stirring and reacting for 8min at 58 ℃, filtering and taking filtrate, wherein the mass ratio of the sample to be detected to the water, the potassium chloride and the nicotinamide is 1:12:0.24: 0.06; and (3) concentrating the filtrate at 45 ℃ until the water content is lower than 1% to obtain a solid to be detected, and dissolving the solid to be detected by using an initial mobile phase for UPLC-MS/MS (ultra performance liquid chromatography-mass spectrometry) determination.
Performance testing
1. Analytical methods Effect comparison
Selecting pig lung which is detected to have no sulfanilamide and quinolone veterinary drug residue, injecting a certain amount of sulfanilamide and quinolone veterinary drug into the pig lung, controlling the mass ratio of a single veterinary drug in animal-derived food to be 0.1, 1.0 and 7.0 mu g/kg, and injecting the veterinary drug comprising sulfamethazine, sulfathiazole, sulfaquinoxaline, lomefloxacin, ciprofloxacin and norfloxacin. The samples were treated as in examples and comparative examples, respectively, and UPLC-MS/MS measurements were carried out under the conditions of example 1, and the results are shown in tables 1 to 3, and 5 groups were subjected to parallel tests and averaged.
Tables 1-3 show that, compared with comparative example 1, the extraction rate of examples 1-4 is greatly improved, the test content is closer to the preparation content, the test accuracy is higher, and examples 1-4 also have obvious advantages in low content test, are suitable for trace detection and are obviously superior to the prior art; the extraction yield of examples 1-4 is greatly improved compared to comparative examples 2-4, which shows that the combination of the technical solutions of examples 1-4 has unexpected results.
TABLE 1 comparison of the results of the analytical methods (0.1. mu.g/kg)
TABLE 2 comparison of the results of the analytical methods (1.0. mu.g/kg)
TABLE 3 comparison of the results of the analytical methods (7.0. mu.g/kg)
2. In-assay sample characterization
Selecting pig lung without sulfanilamide and quinolone veterinary drug residues after detection, and injecting a certain content of sulfanilamide veterinary drug into the pig lung, wherein the mass ratio of a single veterinary drug in animal-derived food is controlled to be 7.0 mu g/kg, and the injected veterinary drugs are respectively sulfamethylpyrimidine, sulfathiazole and sulfaquinoxaline. The samples were treated as follows: crushing and drying: crushing and drying at 45 deg.C until the water content is lower than 2%, pulverizing and sieving with 100 mesh sieve; extraction: taking a crushed and dried sample to be detected, adding water, potassium chloride and nicotinamide, stirring and reacting for 8min at 58 ℃, adding a metal organic framework material UIO-66, nano titanium dioxide and polyethylene glycol 2000, stirring and dispersing for 8min, filtering to obtain a filtrate, wherein the mass ratio of the sample to be detected, the water, the potassium chloride, the nicotinamide, the metal organic framework material UIO-66, the nano titanium dioxide and the polyethylene glycol 2000 is 1:12:0.24:0.06:0.014:0.015: 0.015; mixing the filtrate and chitosan according to the mass ratio of 1:0.33, stirring and reacting at 48 ℃ for 8min, filtering to obtain the filtrate, concentrating the filtrate at 45 ℃ until the water content is lower than 1%, obtaining a solid to be tested, and carrying out XRD test. The test results are shown in FIGS. 1 to 3 and tables 4 to 6.
TABLE 4 XRD data for sulfamethazine nicotinamide eutectic (relative to FIG. 1, molar ratio 1: 1)
TABLE 5 XRD data for sulfathiazole nicotinamide eutectic (relative to FIG. 2, molar ratio 1: 1)
TABLE 6 XRD data for sulfaquinoxaline nicotinamide co-crystal (molar ratio 1:1, relative to FIG. 3)
The above are only typical examples of the present invention, and besides, the present invention may have other embodiments, and all the technical solutions formed by equivalent substitutions or equivalent changes are within the scope of the present invention as claimed.
Claims (1)
1. A high-flux analysis method for chemical residual substances in food comprises sample pretreatment, standard working solution preparation and UPLC-MS/MS measurement which are sequentially arranged,
(1) sample pretreatment
Pulverizing and drying
Taking animal-derived food as a sample to be detected, concentrating the sample to be detected at 40-50 ℃ until the water content is lower than 2% if the sample to be detected is liquid, crushing and sieving the concentrated sample by a 50-100-mesh sieve; if the sample to be detected is solid, stirring and drying the sample at 40-50 ℃ until the water content is lower than 2%, and crushing and sieving the sample by a 50-100-mesh sieve;
extraction of
Taking a crushed and dried sample to be detected, adding water, potassium chloride and nicotinamide, stirring and reacting for 5-10 min at 55-60 ℃, adding a metal organic framework material UIO-66, nano titanium dioxide and polyethylene glycol 2000, stirring and dispersing for 5-10 min, filtering and taking a filtrate, wherein the mass ratio of the sample to be detected, the water, the potassium chloride, the nicotinamide, the metal organic framework material UIO-66, the nano titanium dioxide and the polyethylene glycol 2000 is 1: 10-15: 0.2-0.3: 0.05-0.08: 0.01-0.02; mixing the filtrate with chitosan according to a mass ratio of 1: 0.3-0.4, stirring and reacting at 45-50 ℃ for 5-10 min, filtering to obtain the filtrate, concentrating the filtrate at 40-50 ℃ until the water content is lower than 1% to obtain a solid to be detected, dissolving the solid to be detected with an initial mobile phase, and using the solid to be detected for UPLC-MS/MS determination;
(2) standard working solution preparation
Accurately weighing all target veterinary drug standard products, preparing 1000mg/l standard stock solution by using initial mobile phase, diluting the standard stock solution to 5 concentration points by using the initial mobile phase, and taking the 5 concentration points as standard working solution; the target veterinary drug is selected from sulfamethazine, sulfathiazole and/or sulfaquinoxaline;
(3) UPLC-MS/MS assay
Chromatographic conditions are as follows: a Waters Acquity UPLC BEH C18 chromatographic column, wherein the mobile phase a is methanol, the mobile phase B is a 1wt% formic acid aqueous solution, and the elution mode is gradient elution; the gradient elution procedure was, by volume: 0-2.0 min, 10% of mobile phase A +90% of 1wt% of formic acid aqueous solution, 2.1-8.0 min, 30% of mobile phase A +70% of 1wt% of formic acid aqueous solution, 8.1-14.0 min, 90% of mobile phase A +10% of 1wt% of formic acid aqueous solution, 14.1-16.0 min, 10% of mobile phase A +90% of 1wt% of formic acid aqueous solution;
mass spectrum conditions: ESI + of electrospray ion source, temperature source is 110 ℃, desolventizing temperature is 350 ℃, and desolventizing air flow velocity is 600 L.h-1The temperature of the reverse blowing air flow of the taper hole is 50 L.h-1The mass spectrum scanning method is a multi-reaction detection scanning method with multiple time periods.
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