CN108303478B - Method for measuring nitroimidazole residues in royal jelly by high performance liquid chromatography tandem mass spectrometry - Google Patents
Method for measuring nitroimidazole residues in royal jelly by high performance liquid chromatography tandem mass spectrometry Download PDFInfo
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Abstract
The invention discloses a method for detecting nitroimidazole residues in royal jelly by high performance liquid chromatography tandem mass spectrometry, which comprises a royal jelly sample treatment process, wherein the royal jelly sample treatment process comprises the following steps: adding a temporary use solution of a deuterated internal standard of metronidazole into a royal jelly sample, and adding an organic solvent for vortex and dissolution; adding a protein precipitator for vortex and dissolution, and then centrifuging to obtain an upper inorganic layer; adding a pH regulator into the inorganic layer to regulate the pH, then adding ethyl acetate to extract to obtain an organic layer, and drying by nitrogen; then, ultrasonically dissolving the sample solution by using a mobile phase, adding n-hexane, performing vortex degreasing, centrifuging to obtain a mobile phase layer, and filtering the mobile phase layer by using a filter membrane to obtain an on-machine detection sample solution; one of the protein precipitant and the pH adjustor is an acid and the other is a base. The invention has the beneficial effects that: the method can avoid coating nitroimidazole drugs by protein precipitation, and further improve the sensitivity of the method.
Description
Technical Field
The invention relates to a detection method, in particular to a method for detecting nitroimidazole residues in royal jelly by high performance liquid chromatography-tandem mass spectrometry.
Background
Nitroimidazoles are veterinary drugs containing an imidazole ring with a nitro group attached to the fifth position of the molecule, and are often used to prevent and treat certain pathogenic bacteria and protozoan diseases. Because nitroimidazoles have potential carcinogenic, teratogenic, mutagenic and genotoxic properties, drug residues in animal-derived foods of prescribed drugs such as those in countries of the European Union and Japan cannot be detected, i.e., are below the detection limit of the detection method. The royal jelly is also a medicinal animal-derived food, but the matrix is complex, the sample is difficult to purify, and the accuracy of the measurement of the nitroimidazole medicines in the royal jelly is not high.
Chinese patent publication No. CN101865887A discloses a method for measuring nitroimidazole residues in royal jelly by high performance liquid chromatography tandem mass spectrometry. The method adopts HClO with the volume concentration of 2 percent4Precipitating protein, completely precipitating protein, having low ion inhibition effect, adjusting the pH value of the supernatant to 8.8 by using NaOH solution with the concentration of 1mol/L, back-extracting the target compound by using ethyl acetate in the environment with the pH value of 8.8, easily drying the back-extraction liquid, and having unique sample purification method and simple processThe method is rapid, the use amount of a solvent is not increased, a phosphoric acid buffer solution is not used, and the sensitivity of the method is greatly improved.
However, when HClO is used4During the process of precipitating the protein, due to HClO4The protein precipitate generated by the addition of the nitroimidazole medicament can wrap the nitroimidazole medicament, so that the nitroimidazole medicament is difficult to extract and needs to be improved.
Disclosure of Invention
The invention aims to provide a method for measuring nitromidazole residue in royal jelly by high performance liquid chromatography tandem mass spectrometry. The method can avoid the situation that the nitroimidazole drugs are difficult to extract due to the fact that the nitroimidazole drugs are wrapped by protein precipitates, and further improves the sensitivity of the method.
The technical purpose of the invention is realized by the following technical scheme:
a method for measuring nitroimidazole residues in royal jelly by high performance liquid chromatography tandem mass spectrometry comprises a standard solution preparation process, a royal jelly sample treatment process, a standard curve making process and a royal jelly sample detection process, wherein the royal jelly sample treatment process comprises the following steps:
adding a temporary use solution of a deuterated internal standard of metronidazole into a royal jelly sample, and adding an organic solvent for vortex and dissolution;
adding a protein precipitator for vortex and dissolution, wherein the organic solvent is at the lower layer, the protein precipitator is at the upper layer, and then centrifuging to obtain an upper inorganic layer;
adding a pH regulator into the inorganic layer to regulate the pH, then adding ethyl acetate to perform vortex and liquid-liquid extraction, adding ethyl acetate into the inorganic layer again to perform vortex and liquid-liquid extraction, combining organic layers obtained by two extractions, and performing nitrogen blow-drying;
then, ultrasonically dissolving the sample solution by using a mobile phase, adding n-hexane, performing vortex degreasing, centrifuging to obtain a mobile phase layer, and filtering the mobile phase layer by using a filter membrane to obtain an on-machine detection sample solution;
one of the protein precipitant and the pH adjustor is an acid and the other is a base.
By adopting the technical scheme, the main component of the royal jelly is protein, the royal jelly is dissolved by utilizing an organic solvent, and the protein in the royal jelly is precipitated by using a protein precipitator. Because the density of the organic solvent is greater than that of the protein precipitant and the organic solvent is immiscible, the organic solvent is located in the lower layer and the protein precipitant is located in the upper layer. The protein sinks after forming the protein precipitate in the organic layer, and the nitroimidazole drugs enter the inorganic layer, so that the nitroimidazole drugs are prevented from being wrapped by the protein precipitate in the process of forming the protein precipitate in the organic layer, the extraction of the nitroimidazole drugs is promoted, and the sensitivity of the method is improved. The protein precipitant is acid or alkali, and because the nitroimidazole drugs are amphoteric, the protein precipitant can react with the nitroimidazole drugs, so that the nitroimidazole drugs are promoted to be extracted by the protein precipitant, and the sensitivity of the method is improved.
The invention is further configured to: after adding the protein precipitant and before centrifuging, adding ammonium acetate solution for vortex and dissolving.
By adopting the technical scheme, the ammonium acetate solution is used as a neutral salt solution, and the salting-out of the protein in the royal jelly can be promoted.
The invention is further configured to: after the inorganic layer is adjusted in pH and before the ethyl acetate is added, sodium chloride is added to the inorganic layer, and ethyl acetate is added after the sodium chloride is dissolved.
By adopting the technical scheme, the addition of the sodium chloride can further precipitate the residual protein from the royal jelly in the inorganic layer, and the influence of ethyl acetate on the extraction of the nitroimidazole medicaments is avoided.
The invention is further configured to: the pH of the inorganic layer was adjusted to 8.8 with a pH adjuster.
By adopting the technical scheme, when the pH value is too high or too low, the nitroimidazole drugs are in a charged state, and the extraction efficiency of the ethyl acetate on the nitroimidazole drugs is poor.
The invention is further configured to: the organic solvent is one of dichloromethane, trichloromethane and carbon tetrachloride.
By adopting the technical scheme, the dichloromethane, the trichloromethane and the tetrachloromethane are common organic solvents, are insoluble in water, have higher density than water, do not react with acid and alkali, have better solubility for nitroimidazoles, and are cheap and easy to obtain.
The invention is further configured to: the acid is selected from hydrochloric acid and sulfuric acid.
By adopting the technical scheme, the hydrochloric acid and the sulfuric acid are common acids, are low in price and easy to obtain, and reduce the cost.
The invention is further configured to: the alkali is selected from one of sodium hydroxide and potassium hydroxide.
By adopting the technical scheme, the sodium hydroxide and the potassium hydroxide are common alkali, are cheap and easily obtained, and reduce the cost.
In conclusion, the invention has the following beneficial effects:
1. the main component of royal jelly is protein, the royal jelly is dissolved by organic solvent, and the protein in the royal jelly is precipitated by protein precipitator. Because the density of the organic solvent is greater than that of the protein precipitant and the organic solvent is immiscible, the organic solvent is located in the lower layer and the protein precipitant is located in the upper layer. The protein sinks after forming the protein precipitate in the organic layer, and the nitroimidazole drugs enter the inorganic layer, so that the nitroimidazole drugs are prevented from being wrapped by the protein precipitate in the process that the protein precipitate is formed in the organic layer, the extraction of the nitroimidazole drugs is promoted, and the sensitivity of the method is improved;
2. the protein precipitator is acid or alkali, and because the nitroimidazole drugs are amphoteric, the protein precipitator can react with the nitroimidazole drugs, so that the nitroimidazole drugs are promoted to be extracted by the protein precipitator, and the sensitivity of the method is improved;
3. the ammonium acetate solution is used as neutral salt solution, and can promote salting-out of protein in Lac Regis Apis.
Drawings
FIG. 1 is a total ion flow diagram of the determination of nitroimidazole residues in royal jelly by LC/MS/MS when a standard concentration of 10 mug/kg is added to a royal jelly negative sample in the embodiment of the invention;
FIG. 2 is an ion flow diagram of the extraction of the nitromidazole residue in royal jelly measured by LC/MS/MS when the standard concentration of 0.2 mug/kg is added to a royal jelly negative sample in the embodiment of the invention.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings.
TABLE 1 proportioning tables for examples 1-5
Specific procedure for examples 1-5:
referring to fig. 1 and 2, a method for measuring nitroimidazole residues in royal jelly by high performance liquid chromatography tandem mass spectrometry, which uses raw materials including Metronidazole, CAS: [443-48-1] with purity > 99.4%; metronidazole, ronidazole, CAS: [7681-76-7], purity > 99.0%; dimethylnitroimidazole, dimetridazole, CAS: [551-92-8], purity > 98.5%; d3-dimethylnitroimidazole, Dimetridazole-D3, CAS: 64678-69-9, purity > 98%; pesticide residue grade ethyl acetate, acetonitrile, dichloromethane, trichloromethane and tetrachloromethane; sodium chloride, sodium hydroxide and potassium hydroxide were used as analytical grade; is high grade pure n-hexane; acetonitrile and formic acid which are pure in liquid phase chromatography; water; a mobile phase. Wherein metronidazole, metronidazole and D3-metronidazole are all from Dr.Ehrenstontorfer, Germany; the organic phase in the mobile phase is acetonitrile, the aqueous phase contains formic acid with the volume concentration of 0.1%, and the volume ratio of the organic phase to the aqueous phase in the mobile phase is 3: 97, a stabilizer; the water used was double distilled water.
The equipment used by the method comprises an Agilem triple quadrupole tandem mass spectrometer; agilent 1290 high performance liquid chromatograph: the system is provided with a binary pump, an online degasser, an automatic sample injector and analysis data processing software; an AL204 analytical balance; PHS-3C thunder magnetic precision pH meter; shanghai Luxiang instrument centrifuge, Inc. low-speed desk type large-capacity centrifuge; HSC-24B nitrogen blower of Hengoaken technology development Limited, Tianjin. Wherein the high performance liquid chromatograph is Agilem 1290 Infinity II, the chromatographic column is Intersil ODS C8-3, the specification of the chromatographic column is 2.1 × 150mm, 3 μm or equivalent, and the sample injection amount is 20 μ l; the triple quadrupole tandem mass spectrometer IS 6460C, the sheath gas temperature in the triple quadrupole tandem mass spectrometer IS 375 ℃, the flow rate IS 111/min, the nozzle voltage IS 45psi, the capillary tube voltage (IS) IS 3900.00V, and the ionization method IS in a positive ion mode.
The method comprises a standard solution preparation process, a royal jelly sample treatment process, a standard curve making process and a royal jelly sample detection process.
The standard solution was prepared as follows: a. preparing a mixed storage standard solution: weighing 10mg of metronidazole, 10mg of metronidazole and 10mg of metronidazole, placing the weighed materials in a 10ml volumetric flask, and fixing the volume to 10ml by using acetonitrile to prepare a mixed storage standard solution with the concentration of the metronidazole, the metronidazole and the metronidazole being 1000 mg/L. b. Preparing a mixed intermediate standard solution: and (b) taking 100 mu L of the mixed stock standard solution in the step (a), placing the mixed stock standard solution in a 10ml volumetric flask, and using acetonitrile to make the volume to 10ml to prepare a mixed intermediate standard solution with the concentration of 10 mg/L. c. Preparing a deuterated internal standard of metronidazole: weighing 10mg of D3-metronidazole, placing the weighed solution in a 10ml volumetric flask, metering the volume to 10ml by using acetonitrile to prepare 1000 mg/L-metronidazole deuterated stock solution, placing 100 mu L of the metronidazole deuterated stock solution in the 10ml volumetric flask, and metering the volume to 10ml by using acetonitrile to prepare 10 mg/L-metronidazole deuterated internal standard intermediate solution. d. Preparing a temporary standard use solution: and c, preparing the mixed intermediate standard solution in the step b into a first temporary standard use solution with the concentration of 200 mu g/kg, a second temporary standard use solution with the concentration of 20 mu g/kg and a third temporary standard use solution with the concentration of 10 mu g/kg by using water, and preparing the intermediate solution of the deuterated internal standard of the dinucleomidazole in the step c into a temporary use solution of the deuterated internal standard of the diniconazole with the concentration of 100 mu g/kg by using water.
The royal jelly sample treatment process comprises the following steps:
a. 10g of royal jelly sample is placed in a No. 100ml centrifugal plastic bottle, 100ul of the deuterated internal standard solution of the metronidazole with the concentration of 100 mug/kg is added into the No. 100ml centrifugal plastic bottle, and 10ml of organic solvent is added into the No. 100ml centrifugal plastic bottle for vortex and dissolution;
b. adding a protein precipitator for vortex and dissolution, adding 20mmol/L ammonium acetate solution for vortex and dissolution, wherein the organic solvent is at the lower layer, the protein precipitator is at the upper layer, and then centrifuging to obtain an upper inorganic layer;
c. placing an inorganic layer in a No. two 100ml centrifugal plastic bottle, adding a pH regulator into the inorganic layer to regulate the pH to 8.8, adding 2.0g of sodium chloride into the inorganic layer, adding 10ml of ethyl acetate after the sodium chloride is dissolved, carrying out vortex and liquid-liquid extraction, adding 5ml of ethyl acetate into the inorganic layer again, carrying out vortex and liquid-liquid extraction, combining organic layers obtained by two extractions, placing the organic layer in a 20ml plastic centrifuge tube, and carrying out nitrogen blow-drying at 35 ℃;
d. then adding 1ml of mobile phase into a 20ml plastic centrifuge tube, carrying out ultrasonic dissolution, adding 2ml of n-hexane into the 20ml plastic centrifuge tube, carrying out vortex and degreasing, then carrying out centrifugation for 2min at the rotation speed of 800rpm to obtain a mobile phase layer, and filtering the mobile phase layer through a 0.22 mu m filter membrane to obtain an on-machine detection sample solution;
in the standard curve making procedure, 6 parts of negative royal jelly samples with the weight of 10.0g are weighed and respectively placed in a first reagent bottle, a second reagent bottle, a third reagent bottle, a fourth reagent bottle, a fifth reagent bottle and a sixth reagent bottle, and the negative royal jelly samples used in the invention are common knowledge to technicians in the field. Then adding 10ml of water into the first reagent bottle and mixing uniformly to prepare a first negative queen bee serous fluid; adding 100 mul of No. three temporary standard use solution with the concentration of 10 mug/kg and 10ml of water into a No. two reagent bottle, and uniformly mixing to prepare No. two negative queen bee serous fluid; adding 500 mul of No. three temporary standard use solution with the concentration of 10 mug/kg and 10ml of water into a No. three reagent bottle, and uniformly mixing to prepare No. three negative queen bee serous fluid; adding 1000 mul of second temporary standard use solution with the concentration of 20 mug/kg and 10ml of water into a fourth reagent bottle, and uniformly mixing to prepare fourth negative queen bee serum; adding 500 mul of the first temporary standard use solution with the concentration of 200 mug/kg and 10ml of water into a fifth reagent bottle, and uniformly mixing to prepare a fifth negative queen bee serous fluid; a number six negative queen bee serum was prepared by adding 1000. mu.l of the first temporary standard stock solution having a concentration of 200. mu.g/kg and 10ml of water to a number six reagent bottle and mixing them well. And then, respectively using the first negative queen bee serous fluid, the second negative queen bee serous fluid, the third negative queen bee serous fluid, the fourth negative queen bee serous fluid, the fifth negative queen bee serous fluid and the sixth negative queen bee serous fluid to replace the royal jelly sample liquid in the royal jelly sample treatment process, repeating the step b in the royal jelly sample treatment process to respectively prepare the first standard liquid, the second standard liquid, the third standard liquid, the fourth standard liquid, the fifth standard liquid and the sixth standard liquid, for example, using the first negative queen bee serous fluid to replace the royal jelly sample liquid in the royal jelly sample treatment process, and repeating the step b in the royal jelly sample treatment process to prepare the first standard liquid. In the present example, the concentrations of the first standard solution, the second standard solution, the third standard solution, the fourth standard solution, the fifth standard solution and the sixth standard solution were 0. mu.g/kg, 0.1. mu.g/kg, 0.5. mu.g/kg, 2. mu.g/kg, 10. mu.g/kg and 20. mu.g/kg, respectively. And finally, the first standard solution, the second standard solution, the third standard solution, the fourth standard solution, the fifth standard solution and the sixth standard solution are subjected to a high performance liquid chromatograph and a triple quadrupole tandem mass spectrometer to obtain a standard curve. The HPLC adopts a liquid phase gradient program, the table 2 is a liquid phase gradient elution program table of the HPLC, and the reference mass spectrum condition of the triple quadrupole tandem mass spectrometer for the residue of the nitroimidazoles is shown in the table 3.
TABLE 2 high performance liquid chromatograph liquid phase gradient elution schedule
TABLE 3 Mass Spectrometry reference conditions for Triplex quadrupole tandem Mass spectrometer for Nitro imidazole drug residues
Note: the quantitative ions are underlined and in bold in the table.
It should be noted that the hplc and the triple quadrupole tandem mass spectrometer of the present invention are prior arts, and the operations of the hplc and the triple quadrupole tandem mass spectrometer are well known to those skilled in the art, and therefore, detailed descriptions thereof are omitted here.
In the royal jelly sample detection process, the residual quantity of nitroimidazole drugs in the royal jelly is measured by passing the on-machine detection sample liquid prepared in the royal jelly sample treatment process through a high performance liquid chromatograph and a triple quadrupole tandem mass spectrometer and combining with a standard curve obtained in the standard curve preparation process; the detection limit of the method is 0.05 mu g/kg of metronidazole, 0.1 mu g/kg of metronidazole and 0.1 mu g/kg of metronidazole.
The linear range, detection limit, recovery rate and precision of the present invention were analyzed to prepare 27 kinds of residual standard solutions, which were then subjected to sample injection measurement according to the chromatographic conditions set in the method. Using y to represent peak area (A), using x to represent concentration C (mu g/kg), using EXCEL software to obtain regression equation and linear correlation coefficient, obtaining linear range between 0.1 mu g/kg and 20 mu g/kg, correlation coefficient between 0.9995 and 0.9997, determining three residual detection limits according to concentration corresponding to signal-to-noise ratio S/N-3: 0.015 mu g/kg of metronidazole, 0.03 mu g/kg of metronidazole and 0.03 mu g/kg of metronidazole. Determining the quantitative limits of three residues according to the concentration corresponding to the signal-to-noise ratio S/N-10: 0.05 mu g/kg of metronidazole, 0.1 mu g/kg of metronidazole and 1 mu g/kg of metronidazole O.
The residual standard substances with 3 concentrations are respectively added into the royal jelly negative samples, the samples are processed and measured according to the method, the recovery rate and the relative standard deviation of the method are determined, and the results are shown in table 4.
TABLE 4 Linear Range, detection Limit, recovery, precision, and detection Limit of methods (n ═ 3)
The present embodiment is only for explaining the present invention, and it is not limited to the present invention, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present invention.
Claims (4)
1. A method for measuring nitroimidazole residues in royal jelly by high performance liquid chromatography tandem mass spectrometry comprises a standard solution preparation process, a royal jelly sample treatment process, a standard curve making process and a royal jelly sample detection process, and is characterized in that: the royal jelly sample treatment process comprises the following steps:
adding a temporary use solution of a deuterated internal standard of metronidazole into a royal jelly sample, and adding an organic solvent for vortex and dissolution;
adding a protein precipitator for vortex and dissolution, wherein the organic solvent is at the lower layer, the protein precipitator is at the upper layer, and then centrifuging to obtain an upper inorganic layer;
adding a pH regulator into the inorganic layer to regulate the pH, then adding ethyl acetate to perform vortex and liquid-liquid extraction, adding ethyl acetate into the inorganic layer again to perform vortex and liquid-liquid extraction, combining organic layers obtained by two extractions, and performing nitrogen blow-drying;
then, ultrasonically dissolving the sample solution by using a mobile phase, adding n-hexane, performing vortex degreasing, centrifuging to obtain a mobile phase layer, and filtering the mobile phase layer by using a filter membrane to obtain an on-machine detection sample solution;
one of the protein precipitant and the pH adjuster is an acid and the other is a base;
the organic solvent is one of dichloromethane, trichloromethane and carbon tetrachloride;
the acid is selected from one of hydrochloric acid and sulfuric acid; the alkali is selected from one of sodium hydroxide and potassium hydroxide.
2. The method for detecting the nitroimidazole residues in the royal jelly by the high performance liquid chromatography-tandem mass spectrometry as claimed in claim 1, which is characterized in that: after adding the protein precipitant and before centrifuging, adding ammonium acetate solution for vortex and dissolving.
3. The method for detecting the nitroimidazole residues in the royal jelly by the high performance liquid chromatography-tandem mass spectrometry as claimed in claim 1, which is characterized in that: after the inorganic layer is adjusted in pH and before the ethyl acetate is added, sodium chloride is added to the inorganic layer, and ethyl acetate is added after the sodium chloride is dissolved.
4. The method for detecting the nitroimidazole residues in the royal jelly by the high performance liquid chromatography-tandem mass spectrometry as claimed in claim 1, which is characterized in that: the inorganic layer pH was adjusted to pH =8.8 with a pH adjuster.
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| CN101865887A (en) * | 2010-05-24 | 2010-10-20 | 杭州蜂之语蜂业股份有限公司 | Method for detecting nitromidazole residue in royal jelly by using high performance liquid chromatography tandem mass spectrum |
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| CN101865887A (en) * | 2010-05-24 | 2010-10-20 | 杭州蜂之语蜂业股份有限公司 | Method for detecting nitromidazole residue in royal jelly by using high performance liquid chromatography tandem mass spectrum |
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Denomination of invention: Determination of Nitroimidazole Residues in Royal Jelly by High Performance Liquid Chromatography Tandem Mass Spectrometry Effective date of registration: 20221026 Granted publication date: 20210209 Pledgee: Bank of Hangzhou Co.,Ltd. Fuyang Jiangnan Shopping Mall Small and Micro Enterprises Exclusive Sub branch Pledgor: HANGZHOU KANGLI FOOD Co.,Ltd. Registration number: Y2022980019749 |