CN113156042B - Method for screening sulfonamide residues in goat milk - Google Patents
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Abstract
The invention relates to a method for screening sulfonamide residues in goat milk, which comprises the steps of pretreating goat milk with mixed aqueous solution of acetic acid and acetonitrile, anhydrous magnesium sulfate and anhydrous sodium acetate; adjusting the pH value of the obtained supernatant to 2-6, adding a dispersed solid phase adsorbent prepared from porous graphene and multi-walled carbon nanotubes, performing vortex, centrifuging, separating the obtained supernatant, adding an eluent, uniformly mixing, centrifuging, evaporating the supernatant to dryness, re-dissolving with an ammonium formate aqueous solution to obtain a solution to be detected, simultaneously using blank goat milk to obtain a solution to be detected containing a standard substance of the sulfonamides, and analyzing the two solutions to obtain a quantitative ion chromatographic peak, corresponding retention time, a molecular ion mass-to-charge ratio and a fragment ion mass-to-charge ratio; and finally, comparing the information to obtain the peak area of the quantitative ion chromatographic peak of each sulfonamide, and calculating the concentration of each sulfonamide in the goat milk by combining a matrix matching mixing standard working curve.
Description
Technical Field
The invention belongs to the technical field of food safety detection, and particularly relates to a method for screening sulfonamide residues in goat milk.
Background
The sulfanilamide antibiotics are antibiotics containing sulfanilamide structures, have irreplaceable effects in the development of animal husbandry, are widely used due to the fact that the sulfanilamide antibiotics can promote animal growth, improve feed conversion rate, prevent and treat various diseases, reduce death rate and improve animal product quality, however, the drugs are used excessively or abused unreasonably to cause poisoning of sensitive people, accumulate toxicity, even generate drug resistance and bring harm to human health.
The existing multi-residue detection method comprises a detection method liquid chromatogram-mass spectrum/mass spectrum method for residual amounts of multiple alkaline drugs in SN/T2624-2010 animal-derived food, a determination method liquid chromatogram-mass spectrum/mass spectrum method for residual amounts of multiple acidic and neutral drugs in SN/T2443-2010 import and export animal-derived food, a detection method liquid chromatogram-mass spectrum/mass spectrum method for residual amounts of multiple forbidden drugs in SN/T3235-2012 export animal-derived food and the like, and the liquid chromatogram-tandem mass spectrum method has the advantages of high sensitivity and high selectivity and has become a mainstream method for synchronously detecting multiple veterinary drug residues in complex animal tissue samples.
In view of the complexity of animal-derived food matrices, the QuEChERS (Quick, easy, chemical, effective, rugged and Safe) method is widely applied to veterinary drug residue detection, but before instrumental analysis, a purifying agent or a solid phase extraction column is often used for purification, and the operation is time-consuming and high in cost.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides the method for screening the sulfonamide residues in the goat milk, which is accurate and reliable, reduces the operation cost and time for sample pretreatment, improves the analysis sensitivity and accuracy in a complex food matrix, and has good application prospect in screening the animal-derived food matrix veterinary drug multi-residue.
The invention is realized by the following technical scheme:
a method for screening sulfonamide residues in goat milk comprises the following steps:
the dispersed solid phase adsorbent is prepared by the following steps:
uniformly mixing the dispersion liquid of the porous graphene and the dispersion liquid of the multi-walled carbon nano tube, wherein the mass ratio of the porous graphene to the multi-walled carbon nano tube is (550-650): (275-325) obtaining a mixed system a, and drying a filter cake obtained by suction filtration of the mixed system a to obtain a dispersed solid phase adsorbent;
step 3, uniformly mixing the mixed system, centrifuging to obtain a supernatant C, evaporating the supernatant C to dryness, re-dissolving the evaporated supernatant C with an ammonium formate aqueous solution to obtain a to-be-detected liquid a, and analyzing the to-be-detected liquid a by using ultra-high performance liquid chromatography and quadrupole electrostatic field orbital ion trap mass spectrometry in sequence to obtain a plurality of groups of information formed by a plurality of target analytes;
replacing the goat milk in the step 1 with goat milk without sulfanilamide drugs, repeating the step 1-2 to obtain a mixed system b, adding a standard solution containing standard substances of the sulfanilamide drugs to be analyzed into the mixed system b to obtain a liquid b to be detected, and analyzing the liquid b to be detected by using ultra-high performance liquid chromatography and quadrupole electrostatic field orbit ion trap mass spectrometry in sequence to obtain a plurality of groups of information formed by the standard substances of the sulfanilamide drugs;
each group of information comprises a quantitative ion chromatographic peak and corresponding retention time, as well as a molecular ion mass-to-charge ratio and a fragment ion mass-to-charge ratio;
and 4, comparing each group of information corresponding to each sulfonamide with each group of information corresponding to the target analyte to obtain the peak area of the quantitative ion chromatographic peak of each sulfonamide in the goat milk, and finally, calculating the concentration of each sulfonamide in the goat milk according to the matrix matching mixing standard working curve of each sulfonamide standard substance.
Preferably, in the step 1, a mixed aqueous solution of acetic acid and acetonitrile is added into goat milk, anhydrous magnesium sulfate and anhydrous sodium acetate are added after vortex, vortex and oscillation are sequentially performed, then the obtained mixed solution is stood to obtain a supernatant A, in the mixed aqueous solution of acetic acid and acetonitrile, the volume of acetic acid accounts for 1% of acetonitrile, and the ratio of the total volume of acetic acid and acetonitrile to the volume of water is 21.
Preferably, the porous graphene in step 2 is prepared by the following process:
according to (0.8-1.2) g: (20-25) mL, adding 2000-3000 mesh graphite powder into concentrated sulfuric acid, cooling to 0-4 ℃, and adding KMnO under stirring 4 Adding ultrapure water until the mixed solution is pasty dark green, and adding H 2 O 2 Removing unreacted KMnO in solution 4 Filtering, washing and drying, and performing microwave irradiation on the obtained product for 5-10s at 600-1000W to obtain the porous graphene.
Preferably, the purity of the multi-wall carbon nano-tube in the step 2 is more than 97%, the diameter is 10-30nm, and the length is 5-15 μm.
Preferably, in the step 2, the porous graphene is added into ethanol, and the porous graphene dispersion liquid is obtained after the porous graphene is sequentially stirred for 20-45min and subjected to ultrasonic treatment for 20-45 min; adding hexadecyl trimethyl ammonium bromide into ethanol, performing ultrasonic treatment for 20-45min, adding the multi-walled carbon nano-tube, and performing continuous ultrasonic treatment for 3-4h to obtain the MWCNTs dispersion liquid.
Preferably, the mass ratio of the dispersed solid-phase adsorbent to the goat milk in the step 2 is 0.08: (14-16).
Preferably, the conditions of the ultra high performance liquid chromatography in the step 3 are as follows:
the column temperature is 30-40 ℃, the mobile phase A is a mixed solution of water, formic acid and ammonium formate, wherein the volume of the formic acid accounts for 1% of the volume of the mixed solution, the concentration of the ammonium formate is 4mmol/L, the mobile phase B is composed of a methanol solution of the formic acid and the ammonium formate, wherein the volume of the formic acid accounts for 0.1% of the volume of the methanol solution of the formic acid and the ammonium formate, and the concentration of the ammonium formate in the methanol solution of the formic acid and the ammonium formate is 4mmol/L;
the gradient elution procedure was: within 0-1min, the proportion of the mobile phase A is 100%, within 1-7min, the proportion of the mobile phase A is linearly reduced from 100% to 0,7-12min, the proportion of the mobile phase A is 0, 12-13min, the proportion of the mobile phase A is linearly increased from 0 to 100%, within 13-15min, the proportion of the mobile phase A is 100%, and the flow speed is 200-400 mu L/min.
Preferably, the conditions of the quadrupole electrostatic field orbital ion trap mass spectrum in step 3 are as follows:
the ion source is ESI +, the flow rate of sheath gas is 13-15L/min, the flow rate of auxiliary gas is 2.5-3.5L/min, the ion source temperature is 40-60 deg.C, the capillary temperature is 310-330 deg.C, the first-stage scanning mode is full scanning mode, the resolution is 65000-75000FWHM, and the target value of automatic gain control is 0.8 × 10 7 -1.2×10 7 The maximum injection time is 200-300ms, and the dynamic background subtraction is set8-12s, the two-stage scanning mode is data dependent scanning, the resolution is set to 15000-20000FWHM, the AGC is set to 4.5 × 10 6 -5.5×10 6 The triggering time after the peak emergence is 3-6s, the maximum injection time is 110-130ms, and the dynamic background subtraction is set to be 8-12s.
Further, when the ion response intensity to be fragmented reaches the intensity threshold of 8.3 × 10 4 In the method, the fragmented target analyte is sent to a high energy collision dissociation collision cell and is collided by three different collision energies, namely 17.5eV, 35.0eV and 52.5eV respectively.
Preferably, in step 4, when the matrix of each sulfanilamide standard substance is established to match the mixed standard working curve, the concentration of the corresponding standard substance in the mixed solution is 1-500 mug/L.
Compared with the prior art, the invention has the following beneficial technical effects:
the invention relates to a method for screening sulfonamide residues in goat milk, which comprises the steps of pretreating goat milk by using a mixed aqueous solution of acetic acid and acetonitrile, anhydrous magnesium sulfate and anhydrous sodium acetate, wherein the obtained supernatant does not contain interfering substances such as fat, protein, pigment and the like in the goat milk, so that the sulfonamide residues are released to the maximum extent, then the pH value of an extracting solution is adjusted to 2-6, and the recovery rate of the sulfonamide is adjusted to a proper range by using a dispersed solid phase adsorbent, wherein the dispersed solid phase adsorbent is prepared by mixing a dispersion liquid of porous graphene and a dispersion liquid of multi-walled carbon nano tubes, and the dispersed solid phase adsorbent combines the advantages of high specific surface area of the graphene and the relatively high density of the multi-walled carbon nano tubes, has high adsorption capacity, can further adsorb and enrich the sulfonamide residues in the supernatant, and is convenient to analyze by using an ultra-performance liquid chromatography and a quadrupole rod orbit ion trap mass spectrometry; and corresponding chromatographic and mass spectrometric analysis is carried out by adding a standard solution containing a standard substance of the sulfonamides to be analyzed into the sheep milk without the sulfonamides, so that the influence of interference substances can be eliminated, each sulfonamide in the sheep milk can be accurately identified by comparing the obtained quantitative ion chromatographic peak, the corresponding retention time, the molecular ion mass-to-charge ratio and the fragment ion mass-to-charge ratio, and finally the concentration of each sulfonamide in the sheep milk can be obtained by matching a mixed standard working curve with the quantitative ion chromatographic peak area of each sulfonamide and the matrix of the corresponding standard substance of the sulfonamides. According to the method, the porous graphene composite multi-walled carbon nano tubes are used as a solid-phase dispersion adsorbent, ultra-high performance liquid chromatography separation and high-resolution data rely on acquisition of mass spectrum detection, compared with the traditional method for determining sulfonamide in complex food goat milk, the sample pretreatment process is simplified, the operation is simpler and more economical, simultaneous screening of sulfonamide residues can be realized through high separation and high resolution of ultra-high performance liquid chromatography tandem mass spectrum, once corresponding parameters are set depending on acquisition of mass spectrum data, optimization of each ion pair parameter is not needed, the operation is simple and convenient, and the method is suitable for daily monitoring of sulfonamide residues in animal food by various food detection mechanisms. The multi-walled carbon nano tube and other adsorbents can be used for enriching the sulfonamide in the water environment, and in order to further improve the recovery rate and the analysis sensitivity, the method directly disperses the adsorbents in the goat milk extracting solution to realize dispersed solid phase extraction, time-consuming operations such as column activation, leaching and the like are not needed, the rapid enrichment of a sample is completed, and the detection cost is reduced.
Drawings
Fig. 1a is an SEM image of porous graphene prepared according to the present invention.
Fig. 1b is an SEM image of the porous graphene composite carbon nanotube prepared according to the present invention.
FIG. 2 shows N of the porous graphene composite carbon nanotube prepared according to the present invention 2 Adsorption-desorption isotherms.
FIG. 3a is a graph showing the effect of the type of adsorbent according to the present invention on the recovery of sulfonamides.
FIG. 3b is a graph showing the effect of the type of elution solvent on the recovery of sulfonamides.
FIG. 3c is a graph showing the effect of pH on sulfonamide recovery according to the present invention.
FIG. 3d is a graph showing the effect of adsorption time on sulfonamide recovery according to the present invention.
FIG. 3e is a graph showing the effect of the resolving volume on sulfonamide recovery according to the present invention.
FIG. 3f is a graph showing the effect of the amount of adsorbent according to the present invention on the recovery of sulfonamides.
Detailed Description
The principles and advantages of the present invention are explained and illustrated below by specific embodiments in order to provide a better understanding of the present invention to those skilled in the art. The following description is exemplary only, and is not intended to limit the scope thereof.
The invention relates to a method for screening sulfonamide residues in goat milk, which adopts a mode of dispersive solid-phase extraction-ultra-high performance liquid chromatography quadrupole electrostatic field orbit ion trap mass spectrum, and comprises the following steps:
1) Preparation and characterization of dispersed solid phase adsorbents
Preparation of Porous Graphene (PG): adding 0.8-1.2g of 2000-3000 mesh graphite powder into 20-25mL of concentrated sulfuric acid, cooling to 0-4 ℃ in ice water bath, stirring with a magnetic stirrer at a stirring speed of 20-30rpm, which is beneficial to H 2 SO 4 Fully contacting with graphite, and slowly adding 2.8-3.2g KMnO 4 Keeping stirring in ice water bath for 1.5-2.5h to avoid temperature exceeding 20 deg.C, wherein the mixed solution is pasty dark green, slowly adding 110-150mL ultrapure water, and making the volume fraction of 1-2mL into 30% 2 O 2 Removing unreacted KMnO in the solution 4 After filtration, the mixture was washed three to five times with 25 to 35mL of 2mol/L hydrochloric acid and ultrapure water, respectively, and vacuum-freeze-dried. The dried substance is irradiated by microwave for 5-10s under the condition of 600-1000W.
Theoretically, the smaller the graphite particle size, the more favorable the graphite particle size is to H 2 SO 4 The doping of (2) is beneficial to the formation of the subsequent porous graphene, but the doping can be 2000-3000 meshes in consideration of the cost.
By adding a proper amount of potassium permanganate, the graphite flake is oxidized to be beneficial to enlarging the interlayer spacing of the graphite, thereby leading to more H 2 SO 4 The molecule gets into graphite interlayer and adsorbs on the graphite lamella, can be favorable to the formation of follow-up graphite alkene with the interlamellar spacing increase of graphite, nevertheless adds too much potassium permanganate, can form the defect structure of many poroids on the graphite lamella, and this leads to H easily 2 SO 4 The molecules rapidly escape from the graphite block under the action of microwave, which is not beneficial to the increase of the interlayer spacing of the graphite sheets; in the microwave radiation process, molecules and groups between graphite sheets are heated, decomposed and gasified, so that van der Waals force between the graphite sheets is overcome to do work outwards, the increase of the distance between the graphite sheets is realized, and the preparation of graphene is realized.
The SEM image of the porous graphene is shown in fig. 1a, and it can be seen from fig. 1a that the porous graphene prepared by the solid-state microwave method has obvious macroporous and mesoporous structures.
MWCNTs @ PG: placing 550-650mg PG in a beaker containing 150-250mL pure ethanol, and mechanically stirring for 20-45min and carrying out ultrasonic treatment for 20-45min in sequence to obtain a uniform PG dispersion liquid. Adding 15-25mg of Cetyl Trimethyl Ammonium Bromide (CTAB) into a beaker containing 150-250mL of pure ethanol, carrying out ultrasonic treatment for 20-45min, adding 275-325mg of multi-walled carbon nanotubes (MWCNTs, purity is more than 97%, diameter is 10-30nm, length is 5-15 μm), and continuously carrying out ultrasonic treatment for 3-4h to obtain the MWCNTs dispersion liquid.
And dropwise adding the PG dispersion into the MWCNTs dispersion, shaking for 20-45min, and carrying out ultrasonic treatment for 0.5-1h, wherein the process is repeated for three to five times. Finally, filtering and vacuum freeze drying to obtain the MWCNTs @ PG compound.
The graphene formed by the steps is very light in weight, can only float on the upper layer of a solvent and is not beneficial to adsorption, the multi-walled carbon nanotube is a relatively good adsorbent, CTAB is a surfactant and has good coordination, so that the addition of the graphene is beneficial to the sufficient and uniform compounding of the graphene and the multi-walled carbon nanotube, and the compounding of the graphene and the multi-walled carbon nanotube combines the advantages of high specific surface area of the graphene and relatively high density of the multi-walled carbon nanotube.
The SEM image of the porous graphene composite carbon nanotube is shown in fig. 1b, and it can be seen from fig. 1b that the carbon nanotube material is wound on the surface of the graphene to form a stable composite.
N of porous graphene composite carbon nanotube 2 The adsorption-desorption isotherms are shown in FIG. 2, and it can be seen that MWCNTs @ PG has typical isotherms of IV and II, indicating that mesopores and macropores coexist, which is consistent with the results of SEMFurther calculated, MWCNTs @ PG has a high specific surface area (108.9 m) 2 g -1 ) And a high pore volume (0.45 cm) 3 g -1 ) And high adsorption capacity is ensured.
2) Pretreatment of goat milk samples
Weighing 14-16g (accurate to 0.01 g) of goat milk into a 50mL centrifuge tube, adding 9-11mL of mixed aqueous solution of acetic acid and acetonitrile, wherein the volume of the acetic acid accounts for 1% of the acetonitrile, the ratio of the total volume of the acetic acid and the acetonitrile to the volume of water is 84, carrying out vortex mixing for 25-35s, adding 5.5-6.5g of anhydrous magnesium sulfate and 1.4-1.5g of anhydrous sodium acetate, carrying out vortex mixing for 25-35s, oscillating for 1min, centrifuging for 4-6min at 3-5 ℃ and 8000-12000r/min, thus removing interfering substances such as fat, protein, pigment and the like in the goat milk and releasing sulfonamide residues to the maximum extent;
transferring the supernatant, adjusting pH to 2-6 with HCl solution, placing in 15.0mL centrifuge tube, adding 80mg MWCNTs @ PG, vortexing for 3-5min, centrifuging for 4.5-5.5min, discarding supernatant, and adding 20mL1% (V: V) NH 4 And (3) ultrasonically treating the OH methanol eluent for 2.5-3.5min, centrifuging for 4.5-5.5min, rotatably evaporating the supernatant, re-dissolving with 1-2mL of 4mM ammonium formate aqueous solution, filtering with a 0.22-micron organic filter membrane, and performing analysis by an instrument.
The multi-walled carbon nanotube composite graphene material has a high specific surface area and has pi-pi adsorption effect on molecules such as sulfanilamide and the like, so that sulfanilamide drugs in supernate are adsorbed and enriched, other impurities are possibly adsorbed in the process, a matrix correction matching curve needs to be established in the subsequent step to eliminate the influence, and the 20mL eluent has a large volume and low target substance concentration, so that the concentration of a target analysis substance is favorably improved by re-dissolving with a small amount of solvent after being evaporated to dryness, and the detection of an instrument is convenient.
The step optimizes the conditions of the dispersed solid phase extraction, and the conditions of the dispersed solid phase extraction which influence the extraction efficiency comprise the types of adsorbents, the pH of samples, the types and the volumes of elution solvents, the extraction time and the dosage of the adsorbents.
The choice of adsorbent has a significant impact on the recovery of the target analyte from a complex matrix. The invention compares the influence of 100mg MWCNTs, 100mg PG and 100mg MWCNTs @ PG on the recovery rate of a blank goat milk sample (goat milk without sulfonamides, which can be obtained by identification) by quantitatively adding 10 mixed standard solutions (the concentrations of which are respectively 100 mug/kg) of sulfonamides, as shown in figure 3a, MWCNTs @ PG has the highest recovery rate for 8 sulfonamides, because MWCNTs @ PG combines the rich pi electronic structure of MWCNTs and the high specific surface area and porous structure of PG, and abundant adsorption sites are provided for sulfonamides.
The elution solvent is an important factor for the complete elution of the analyte, and methanol, 1% (v/v) NH, was investigated in the present invention 4 OH methanol, acetonitrile and 1% (v/v) NH 4 Effect of OH acetonitrile four eluents on recovery of 10 sulfonamides, 1% (v/v) NH, as shown in FIG. 3b 4 The recovery of OH methanol is highest.
Because the sulfanilamide drug molecules have different forms under different pH values, the recovery rate of the sulfanilamide drugs is investigated at the pH values (2,4,6,8, 10) of different samples, the result shows that the recovery rate of 10 sulfanilamide drugs is the highest when the pH value is =4, and the recovery rate of the sulfanilamide drugs is remarkably reduced when the pH value is more than 6, because the sulfanilamide is negatively charged when the sample solution is in an alkaline condition, and the adsorption amount of the sulfanilamide drugs in MWCNTs @ PG is greatly reduced due to the action of electrostatic repulsion, as shown in figure 3 c.
The present inventors examined the effect of extraction time (0-5 min) and volume of resolving solvent (5-25 mL) on recovery, as shown in FIG. 3d and FIG. 3e, with the highest recovery achieved with 3min adsorption time and 20mL resolving solvent.
The present invention examined the effect of different mass (20-100 mg) adsorbents on recovery, as shown in FIG. 3f, 80mg of MWCNTs @ PG could reach the highest recovery.
3) Determination of chromatographic and mass spectrum conditions
Chromatographic conditions are as follows: hypersil Gold aQ C-18 column (specification 100 mm. Times.2.1mm, 1.9 μm, thermo Fisher Scientific Co., U.S.A.), column temperature: 30-40 ℃; the mobile phase A is a mixed solution of water, formic acid and ammonium formate, wherein the volume of the formic acid accounts for 1% of the volume of the mixed solution, and the concentration of the ammonium formate is 4mmol/L: the mobile phase B consists of formic acid and a methanol solution of ammonium formate, wherein the formic acid accounts for 0.1% of the volume of the methanol solution of ammonium formate, and the concentration of the ammonium formate in the methanol solution of ammonium formate is 4mmol/L;
the gradient elution procedure was: within 0-1min (the proportion of the mobile phase A is 100%), within 1-7min (the proportion of the mobile phase A is linearly reduced from 100% to 0), within 7-12min (the proportion of the mobile phase A is 0), within 12-13min (the proportion of the mobile phase A is linearly increased from 0 to 100%), within 13-15min (the proportion of the mobile phase A is 100%), at the flow rate of 200-400 muL/min and at the sampling rate of 5 muL.
Mass spectrum conditions: electrospray ionization (ESI + ion source); the flow rate of the sheath gas is 13-15L/min, and the flow rate of the auxiliary gas is 2.5-3.5L/min; the temperature of the ion source is 40-60 ℃; the capillary temperature is 310-330 ℃. The first-stage scanning mode is full-scan mode, wherein the resolution is set to 65000-75000FWHM and the target value (AGC) of automatic gain control is set to 0.8 × 10 7 -1.2×10 7 The allowable mass error range is 3ppm, the maximum injection time is 200-300ms, and the dynamic background subtraction is set to be 8-12s. The two-stage scanning mode is data dependent scanning, the resolution is set to 15000-20000FWHM, the AGC is set to 4.5 × 10 6 -5.5×10 6 The trigger time after the peak emergence is 3-6s, the maximum injection time is 110-130ms, the dynamic background subtraction is set to be 8-12s, and the TOP 5 mode is selected.
The target analytes to be fragmented are set in a specific information list (i.e. molecular ion, fragment ion m/z values, retention time values, i.e. chromatographic, mass spectral parameters in tables 1, 2 set for a specific target substance) with an allowable mass error range set at 10ppm. When the ion response intensity to be fragmented reaches the intensity threshold of 8.3 multiplied by 10 4 And then sending the ion beam to a high-energy collision dissociation collision pool, respectively colliding by three different collision energies, and finally superposing to obtain a photon ion spectrogram, wherein the collision energies are respectively 17.5eV, 35.0eV and 52.5eV.
The chromatographic and mass spectrometric parameters of the 10 standard substances are shown in tables 1 and 2.
TABLE 1 chromatographic parameters of 10 sulfonamide standard substances
TABLE 2 Mass Spectrometry parameters of 10 sulfonamide standard substances
And (3) establishing a matrix matching mixing standard working curve for each sulfanilamide standard substance, wherein x represents the concentration (mu g/kg) of the standard substance, and the ordinate y represents the peak area of a quantitative ion chromatographic peak of the sulfanilamide standard substance. Transferring 12 parts of sheep milk containing no sulfanilamide 15g each, treating by step 2 until 20mL of 1% (V: V) NH is added 4 And (3) placing the obtained mixed solution in a 50mL volumetric flask until the OH methanol eluent is eluted, blowing the mixed solution to be nearly dry by a vacuum nitrogen blow dryer, respectively adding 10 muL, 20 muL, 40 muL, 80 muL, 100 muL, 200 muL, 400 muL, 800 muL, 1000 muL, 2000 muL, 4000 muL and 5000 muL of sulfanilamide standard substance mixed solution with the concentration of 1000 mug/L into the volumetric flask, respectively adding 5mL of methanol, diluting with 8mmol/L ammonium formate aqueous solution and fixing the volume to scale to prepare corresponding substrate matching standard solutions of 1 mug/L, 2 mug/L, 4 mug/L, 8 mug/L, 10 mug/L, 20 mug/L, 40 mug/L, 80 mug/L, 100 mug/L, 200 mug/L, 400 mug/L and 500 mug/L. The substrate matching standard solution should be prepared immediately, and then the quantitative ion chromatographic peak of the substance to be analyzed is extracted, so that the linear equation as shown in the following table 3 can be obtained, and further, the concentration of the sulfanilamide substance to be determined can be obtained according to the standard curve.
The identification process comprises the following steps: comparison was made with standard materials, including retention time (standard retention time ± 0.5 min), exact molecular ion mass to charge ratio, fragment ion mass to charge ratio, with mass deviation set at 10ppm.
Mass deviation in ppm = | { (experimentally determined m/z-standard substance m/z)/standard substance m/z } × 10 6 |
Taking sulfamethazine as an example, the retention time extracted in an unknown goat milk sample is =5.38min, it is preliminarily determined to be sulfamethazine, it is confirmed to be sulfamethazine by extracting molecular ions m/z =279.09287 (6.63 ppm) and fragment daughter ions m/z =124.02255 (8.06 m) and m/z =96.04519 (8.32 ppm), the corresponding molecular ion chromatogram area is extracted to be 77076.8, and the concentration is 10.7 μ g/kg by y =6675.4x 5650.
4) Methodology feasibility verification (i.e. parameter investigation)
The methodology parameter investigation was according to European Union Standard 2002/657/EC and SANCO/12571/2013.
First, the matrix effect was investigated: the pretreatment technology of the dispersive solid-phase extraction belongs to a broad-spectrum extraction method, and can not completely remove interference co-extraction substances which influence the recovery rate of a target compound, and the structure and the property of the target compound are different, so that the synergistic enhancement or competitive inhibition effect is generated, the ionization efficiency of the target compound is enhanced or inhibited, the response intensity is increased or reduced through mass spectrometry detection of a quadrupole electrostatic field orbital ion trap, and the sensitivity and the accuracy of the method are influenced by the degree of matrix effect.
The results of the target pesticide and veterinary drug compounds are within +/-20% and have weak matrix effects, the absolute values of the results of the target pesticide and veterinary drug compounds are 50% -100% and have strong matrix effects, and the absolute values of the results of the target pesticide and veterinary drug compounds are 20% -50% and have medium matrix effects. The result shows that most sulfanilamide drug matrix effects are within +/-20%, and the purification effect is good.
And secondly, observing a standard curve, a linear range and a correlation coefficient of the method, and when a matrix matching mixed standard working curve is drawn, x represents the concentration (mu g/kg) of the standard substance, and the ordinate y represents the peak area of the quantitative ion chromatographic peak of the exogenous risk substance. The correlation coefficients of the established standard curves are all larger than 0.99, and the standard curves are considered to be reliable. Finally, the quantitative lower limit, the standard addition recovery rate and the precision of the method are examined. The detection limit and the lower limit of quantitation were examined by the determination limit (CC. Alpha.) and the detection capacity (CC. Beta.). When the CC alpha value is equal to or higher than the specific value of the CC alpha in the evaluation index of the European Union 2002/657/EC aiming at the pesticide residue determination method, the alpha error probability is calculated, and the measured sample is considered not to meet the specified conclusion limit; CC beta means that the lowest content of a substance in a sample is detected, identified and quantified by using beta error probability, and the statistical hypothesis of CC alpha and CC beta is similar to the detection limit and the quantification limit. The CC alpha is determined by a calibration curve method, blank milk and dairy product matrixes are used, mixed standard substances are added according to equidistant gradient, after a mass spectrogram is analyzed, the concentration and peak area of an additive standard are plotted, and the CC alpha is equal to 2.33 times of the concentration value on the ordinate axis in response observation plus the corresponding standard deviation of reproducibility. CC beta is 1.64 times of the standard deviation of reproducibility when the value of CC alpha is added with the value of CC alpha. On the basis of the above results, the average recovery rate and the relative standard deviation of various exogenous risk substances were calculated and measured in parallel six times. The result shows that the recovery rate and the relative standard deviation result of all sulfonamides are respectively 75-120% and less than 10%, and the established method has good accuracy and precision.
Since the selected adsorbent has a large specific surface area, a large pore volume and an affinity adsorption to molecules having a benzene ring structure, interfering co-extractives having an influence on the recovery rate of the target compound cannot be completely removed, and it is first necessary to examine the matrix effect. The formula is calculated as follows:
in the formula:
c% -matrix effect;
ss-slope of standard curve of target compound prepared from pure solvent;
slope of standard curve of target compound prepared from Sm-blank matrix.
The results show that the absolute values of the matrix effect of 8 sulfanilamide drugs are between 9.8% and 17.3%, the matrix effect belongs to weak equal matrix effect, the absolute values of the matrix effect of 2 sulfanilamide drugs are 21.5% and 26.4%, the matrix effect belongs to medium matrix effect, and the matrix effect needs to be reduced and the result accuracy needs to be improved by establishing a matrix matching curve. Sulfanilamide in the detection method is in the corresponding concentration range, and the correlation coefficient (R) 2 ) Are all larger than 0.99, and have good linear relation. Table 3 shows that the determination limit (CC. Alpha.) and the detection capacity (CC. Beta.) are 0.01 to 0.25. Mu.g/kg and 0.03 to 0.45. Mu.g/kg, respectively. Addition of CC beta, 2-fold CC beta and4 times of CC beta, three levels of series of mixed standard substance solutions, and the accuracy of the experiment is evaluated through the recovery rate, and the precision is determined through the relative standard deviation of the recovery rate results of 6 parallel experiments. The results in table 4 show that the recovery and RSD results are 75-109% and 0.6-9.3%, respectively, and the established method is good in accuracy and precision.
Table 3 relevant validation parameter results for methodology of 10 sulfanilamide drugs in sheep milk (n = 6)
Table 4 results of recovery and relative standard deviation of 10 sulfanilamide drugs in sheep's milk in parallel experiment (n = 6)
5. Analysis of actual samples
The invention adopts the following parameters to analyze the actual sample:
1) Preparation and characterization of dispersed solid phase adsorbents
Preparing porous graphene: adding 1g 2000 mesh graphite powder into 23mL concentrated sulfuric acid, cooling to 0 deg.C in ice water bath, stirring with magnetic stirrer at 20rpm, and slowly adding 3g KMnO 4 Keeping the temperature from exceeding 20 ℃ and stirring in an ice-water bath for 2 hours, slowly adding 138mL of ultrapure water, and making the volume fraction of 1mL into 30% 2 O 2 Removing unreacted KMnO in the solution 4 After filtration, the reaction mixture was washed five times with 30mL of 2mol/L hydrochloric acid and ultrapure water, respectively, and vacuum-freeze-dried. The dried material was irradiated with microwave at 800W for 5 g.
MWCNTs @ PG: placing 600mg PG in a beaker containing 200mL pure ethanol, and sequentially mechanically stirring for 30min and ultrasonically treating for 30min to obtain a uniform PG dispersion liquid. And adding 20mg of hexadecyl trimethyl ammonium bromide into another beaker containing 200mL of pure ethanol, carrying out ultrasonic treatment for 30min, adding 300mg of multi-walled carbon nanotubes, and carrying out continuous ultrasonic treatment for 3h to obtain the MWCNTs dispersion liquid.
And dropwise adding the PG dispersion into the MWCNTs dispersion, oscillating for 30min, carrying out ultrasonic treatment for 0.5h, repeating the process for three times, and finally carrying out suction filtration and vacuum freeze drying to obtain the MWCNTs @ PG compound.
2) Pretreatment of goat milk samples
Weighing 15g (accurate to 0.01 g) of goat milk into a 50mL centrifuge tube, adding 10mL of mixed aqueous solution of acetic acid and acetonitrile, wherein the volume of the acetic acid accounts for 1% of the acetonitrile, the ratio of the total volume of the acetic acid and the acetonitrile to the volume of water is 84, carrying out vortex mixing for 30s, then adding 6g of anhydrous magnesium sulfate and 1.45g of anhydrous sodium acetate, carrying out vortex mixing for 30s, then oscillating for 1min, and centrifuging for 5min at 4 ℃ and 10000 r/min;
transferring the supernatant, adjusting pH to =4 with HCl solution, placing in a 15.0mL centrifuge tube, adding 80mg MWCNTs @ PG, vortexing for 3min, centrifuging for 5min, discarding the supernatant, and adding 20mL of 1% (V: V) NH 4 And (3) ultrasonically treating the OH methanol eluent for 3min, centrifuging for 5min, rotationally evaporating supernatant, redissolving by using 1mL of 4mM ammonium formate aqueous solution, filtering by using a 0.22-micron organic filter membrane, and waiting for instrumental analysis.
3) Chromatographic and mass spectrum condition determination
Chromatographic conditions are as follows: column temperature: 35 deg.C
Mass spectrum conditions: the flow rate of the sheath gas is 14L/min, and the flow rate of the auxiliary gas is 3L/min; the ion source temperature is 50 ℃; the capillary temperature was 320 ℃. The one-stage scanning mode is full scan mode, in which the resolution is set to 70000FWHM and the target value of Automatic Gain Control (AGC) is set to 1.0 × 10 7 The allowable mass error range is 3ppm, the maximum injection time is 250ms, and the dynamic background subtraction is set to 10s. The two-stage scanning mode is data dependent scanning, the resolution is set to 17500FWHM, and the AGC is set to 5 multiplied by 10 6 The maximum injection time was 120ms and the dynamic background subtraction was set to 10s.
Screening sulfanilamide drug residues in 67 batches of goat milk by the established method, qualitatively screening 10 veterinary drugs in a sample by adopting an accurate mass number and retention time, and combining characteristic fragmentation ion confirmation. Only two positive samples are detected to contain sulfamethazine, the concentration is 10.7 mu g/kg and 22.1 mu g/kg, and the maximum residue limit of veterinary drugs in national standard food GB 31650-2019 for food safety is not exceeded.
The following describes the apparatus, sample, and reagent.
1. Instrument
An UltiMate 3000 series liquid chromatography-Q active mass spectrometer (Thermo corporation, usa), a BCD-193MT refrigerator (kangaka co-creation appliances ltd, anhui), a BSA224S type electronic balance (sytss instruments ltd, beijing sedolis), a PH-070A type constant temperature drying box (huitai instruments ltd, shanghai), a Milli-Q ultra pure water apparatus (Millipore corporation, usa), an Avnti J-26 × PI type high speed refrigerated centrifuge (Beckman Coulter, usa), a variable speed multi-purpose oscillator; vortex mixer model 2T vortex mixer (Scientific Industries, usa).
2. Sample (I)
67 batches of goat milk samples were purchased randomly from a local supermarket.
3. Reagent
Sulfanilamide, sulfathiazole, sulfamethoxypyridazine, sulfamethazine, sulfamethoxazole, sulfamethazine, sulfachloropyridazine, toluoylsulfanilamide, sulfadimethoxine, sulfaquinoxaline standards, available from dr. Cetyl Trimethyl Ammonium Bromide (CTAB), concentrated sulfuric acid, potassium permanganate, graphite (2000 mesh), MWCNTs (purity > 97%, diameter 10-30nm, length 5-15 μm) purchased from Allantin Biotechnology Ltd, concentrated hydrochloric acid, 30% H 2 O 2 Methanol, acetonitrile, formic acid, commercially available from Merck, germany. Acetonitrile, formic acid and ammonium formate (Fisher, usa, chromatographically pure).
The above-described embodiments of the present invention are examples, and any means having the same function and effect as those of the technical idea of the claims of the present invention is included in the present invention.
Claims (2)
1. A method for screening sulfonamide residues in goat milk is characterized by comprising the following steps:
step 1, adding a mixed aqueous solution of acetic acid and acetonitrile into goat milk, adding anhydrous magnesium sulfate and anhydrous sodium acetate after vortex, and sequentially vortex and oscillating, wherein the ratio of the goat milk to the mixed aqueous solution to the anhydrous magnesium sulfate to the anhydrous sodium acetate is (14-16) g: (9-11) mL: (5.5-6.5) g: (1.4-1.5) g, wherein in the mixed aqueous solution of acetic acid and acetonitrile, the volume of acetic acid accounts for 1% of acetonitrile, the ratio of the total volume of acetic acid and acetonitrile to the volume of water is 21;
step 2, adjusting the pH value of the supernatant A to 2-6, adding a dispersed solid phase adsorbent for vortex, wherein the mass ratio of the dispersed solid phase adsorbent to the goat milk is 0.08: (14-16), centrifuging, separating the obtained supernatant B, and adding an eluent, wherein the eluent is NH 4 Mixed solution of OH and methanol, NH 4 The volume ratio of OH to methanol is 1;
the dispersed solid phase adsorbent is prepared by the following processes:
dropping the dispersion liquid of the porous graphene into the dispersion liquid of the multi-wall carbon nanotube drop by drop, oscillating for 20-45min, ultrasonically treating for 0.5-1h, repeating for 3-5 times, wherein the purity of the multi-wall carbon nanotube is more than 97%, the diameter is 10-30nm, the length is 5-15 mu m, and the mass ratio of the porous graphene to the multi-wall carbon nanotube is (550-650): (275-325) to obtain a mixed system a, and drying a filter cake obtained by suction filtration of the mixed system a to obtain a dispersed solid phase adsorbent;
the dispersion liquid of the porous graphene is prepared by the following steps:
according to (0.8-1.2) g: (20-25) mL, adding 2000-3000 mesh graphite powder into concentrated sulfuric acid, cooling to 0-4 ℃, and adding KMnO under stirring 4 ，KMnO 4 The mass ratio of the graphite powder to the graphite powder is (0.8-1.2): (2.8-3.2 g) until the resulting mixed solution is a paste with dark green color, adding ultrapure water, and adding H 2 O 2 Removing unreacted KMnO in solution 4 Filtering, washing and drying, performing microwave irradiation on the obtained product for 5-10s under 600-1000W to obtain porous graphene, adding the porous graphene into ethanol, wherein the proportion of the ethanol to the porous graphene is (150-250) mL: (550-650) mg, and obtaining a porous graphene dispersion liquid after sequentially stirring for 20-45min and carrying out ultrasonic treatment for 20-45 min;
the dispersion liquid of the multi-walled carbon nano-tube is prepared by the following steps:
adding cetyl trimethyl ammonium bromide into ethanol, performing ultrasonic treatment for 20-45min, and adding a multi-walled carbon nanotube, wherein the proportion of the ethanol, the cetyl trimethyl ammonium bromide and the multi-walled carbon nanotube is (150-250) mL: (15-25) mg: (275-325) mg, and continuously performing ultrasonic treatment on the mixture for 3-4h to obtain a dispersion liquid of the multi-wall carbon nano-tube;
step 3, uniformly mixing the mixed system, centrifuging to obtain supernatant C, evaporating the supernatant C to dryness, re-dissolving with an ammonium formate aqueous solution to obtain a solution a to be detected, sequentially analyzing the solution a to be detected by using ultra-high performance liquid chromatography and quadrupole electrostatic field orbital ion trap mass spectrometry, and when the ion response intensity to be fragmented reaches an intensity threshold of 8.3 multiplied by 10 4 When in use, sending the fragmented target analytes to a high-energy collision dissociation collision pool, and respectively colliding with three different collision energies, wherein the collision energies are 17.5eV, 35.0eV and 52.5eV respectively, so as to obtain a plurality of groups of information formed by a plurality of target analytes;
the conditions of the ultra-high performance liquid chromatography are as follows:
the column temperature is 30-40 ℃, the mobile phase A is a mixed solution of water, formic acid and ammonium formate, wherein the volume of the formic acid accounts for 1% of the volume of the mixed solution, the concentration of the ammonium formate is 4mmol/L, the mobile phase B is composed of a methanol solution of the formic acid and the ammonium formate, wherein the volume of the formic acid accounts for 0.1% of the volume of the methanol solution of the formic acid and the ammonium formate, and the concentration of the ammonium formate in the methanol solution of the formic acid and the ammonium formate is 4mmol/L;
the gradient elution procedure was: within 0-1min, the proportion of the mobile phase A is 100%, within 1-7min, the proportion of the mobile phase A is linearly reduced from 100% to 0,7-12min, the proportion of the mobile phase A is 0, 12-13min, the proportion of the mobile phase A is linearly increased from 0 to 100%, within 13-15min, the proportion of the mobile phase A is 100%, and the flow speed is 200-400 mu L/min;
the conditions of quadrupole electrostatic field orbitals ion trap mass spectrometry are as follows:
the ion source is ESI +, the flow rate of sheath gas is 13-15L/min, the flow rate of auxiliary gas is 2.5-3.5L/min, the ion source temperature is 40-60 deg.C, the capillary temperature is 310-330 deg.C, and the first-stage scanning mode is full-scanning modeThe resolution is set to 65000-75000FWHM in full scan mode, and the target value of automatic gain control is 0.8 × 10 7 -1.2×10 7 The maximum injection time is 200-300ms, the dynamic background subtraction is set to 8-12s, the secondary scanning mode is data dependent scanning, the resolution is set to 15000-20000FWHM, and the AGC is set to 4.5 × 10 6 -5.5×10 6 The triggering time after the peak emergence is 3-6s, the maximum injection time is 110-130ms, and the dynamic background subtraction is set to be 8-12s;
replacing the goat milk in the step 1 with goat milk without sulfanilamide drugs, repeating the step 1-2 to obtain a mixed system b, adding a standard solution containing standard substances of the sulfanilamide drugs to be analyzed into the mixed system b to obtain a liquid b to be detected, and analyzing the liquid b to be detected by using ultra-high performance liquid chromatography and quadrupole electrostatic field orbit ion trap mass spectrometry in sequence to obtain a plurality of groups of information formed by the standard substances of the sulfanilamide drugs;
each group of information comprises a quantitative ion chromatographic peak and corresponding retention time, as well as a molecular ion mass-to-charge ratio and a fragment ion mass-to-charge ratio;
and 4, comparing each group of information corresponding to each sulfonamide with each group of information corresponding to the target analyte to obtain the peak area of the quantitative ion chromatographic peak of each sulfonamide in the goat milk, and finally, calculating the concentration of each sulfonamide in the goat milk according to the matrix matching mixing standard working curve of each sulfonamide standard substance.
2. The method for screening sulfonamide residues in sheep milk according to claim 1, wherein in step 4, when the matrix of each sulfonamide standard substance is established to match the mixed standard working curve, the concentration of the corresponding standard substance in the mixed solution is 1-500 μ g/L.
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