CN114791467A - Method and device for detecting content of streptomycin and dihydrostreptomycin in honey - Google Patents
Method and device for detecting content of streptomycin and dihydrostreptomycin in honey Download PDFInfo
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- CN114791467A CN114791467A CN202210384113.0A CN202210384113A CN114791467A CN 114791467 A CN114791467 A CN 114791467A CN 202210384113 A CN202210384113 A CN 202210384113A CN 114791467 A CN114791467 A CN 114791467A
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- dihydrostreptomycin
- streptomycin
- sample
- honey
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- AWBXTNNIECFIHT-XZQQZIICSA-N 2-[(1r,2r,3s,4r,5r,6s)-3-(diaminomethylideneamino)-4-[(2r,3r,4r,5s)-3-[(2s,3s,4s,5r,6s)-4,5-dihydroxy-6-(hydroxymethyl)-3-(methylamino)oxan-2-yl]oxy-4-formyl-4-hydroxy-5-methyloxolan-2-yl]oxy-2,5,6-trihydroxycyclohexyl]guanidine;2-[(1r,2r,3s,4r,5r,6s)-3-( Chemical compound CN[C@H]1[C@H](O)[C@@H](O)[C@H](CO)O[C@H]1O[C@@H]1[C@](CO)(O)[C@H](C)O[C@H]1O[C@@H]1[C@@H](N=C(N)N)[C@H](O)[C@@H](N=C(N)N)[C@H](O)[C@H]1O.CN[C@H]1[C@H](O)[C@@H](O)[C@H](CO)O[C@H]1O[C@@H]1[C@](C=O)(O)[C@H](C)O[C@H]1O[C@@H]1[C@@H](N=C(N)N)[C@H](O)[C@@H](N=C(N)N)[C@H](O)[C@H]1O AWBXTNNIECFIHT-XZQQZIICSA-N 0.000 title claims abstract description 45
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- UCSJYZPVAKXKNQ-HZYVHMACSA-N streptomycin Chemical compound CN[C@H]1[C@H](O)[C@@H](O)[C@H](CO)O[C@H]1O[C@@H]1[C@](C=O)(O)[C@H](C)O[C@H]1O[C@@H]1[C@@H](NC(N)=N)[C@H](O)[C@@H](NC(N)=N)[C@H](O)[C@H]1O UCSJYZPVAKXKNQ-HZYVHMACSA-N 0.000 claims description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 11
- ASXBYYWOLISCLQ-UHFFFAOYSA-N Dihydrostreptomycin Natural products O1C(CO)C(O)C(O)C(NC)C1OC1C(CO)(O)C(C)OC1OC1C(N=C(N)N)C(O)C(N=C(N)N)C(O)C1O ASXBYYWOLISCLQ-UHFFFAOYSA-N 0.000 claims description 8
- ASXBYYWOLISCLQ-HZYVHMACSA-N dihydrostreptomycin Chemical compound CN[C@H]1[C@H](O)[C@@H](O)[C@H](CO)O[C@H]1O[C@@H]1[C@](CO)(O)[C@H](C)O[C@H]1O[C@@H]1[C@@H](NC(N)=N)[C@H](O)[C@@H](NC(N)=N)[C@H](O)[C@H]1O ASXBYYWOLISCLQ-HZYVHMACSA-N 0.000 claims description 8
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- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 2
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- CZWJCQXZZJHHRH-YCRXJPFRSA-N 2-[(1r,2r,3s,4r,5r,6s)-3-(diaminomethylideneamino)-4-[(2r,3r,4r,5s)-3-[(2s,3s,4s,5r,6s)-4,5-dihydroxy-6-(hydroxymethyl)-3-(methylamino)oxan-2-yl]oxy-4-hydroxy-4-(hydroxymethyl)-5-methyloxolan-2-yl]oxy-2,5,6-trihydroxycyclohexyl]guanidine;sulfuric acid Chemical compound OS(O)(=O)=O.OS(O)(=O)=O.OS(O)(=O)=O.CN[C@H]1[C@H](O)[C@@H](O)[C@H](CO)O[C@H]1O[C@@H]1[C@](CO)(O)[C@H](C)O[C@H]1O[C@@H]1[C@@H](N=C(N)N)[C@H](O)[C@@H](N=C(N)N)[C@H](O)[C@H]1O.CN[C@H]1[C@H](O)[C@@H](O)[C@H](CO)O[C@H]1O[C@@H]1[C@](CO)(O)[C@H](C)O[C@H]1O[C@@H]1[C@@H](N=C(N)N)[C@H](O)[C@@H](N=C(N)N)[C@H](O)[C@H]1O CZWJCQXZZJHHRH-YCRXJPFRSA-N 0.000 description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
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- WEEMDRWIKYCTQM-UHFFFAOYSA-N 2,6-dimethoxybenzenecarbothioamide Chemical compound COC1=CC=CC(OC)=C1C(N)=S WEEMDRWIKYCTQM-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 206010002199 Anaphylactic shock Diseases 0.000 description 1
- 241000272201 Columbiformes Species 0.000 description 1
- 238000002965 ELISA Methods 0.000 description 1
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 1
- 206010029155 Nephropathy toxic Diseases 0.000 description 1
- 206010033109 Ototoxicity Diseases 0.000 description 1
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- 208000003455 anaphylaxis Diseases 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- 229960001162 dihydrostreptomycin sulfate Drugs 0.000 description 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 1
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- 231100000262 ototoxicity Toxicity 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- YPJUNDFVDDCYIH-UHFFFAOYSA-N perfluorobutyric acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)F YPJUNDFVDDCYIH-UHFFFAOYSA-N 0.000 description 1
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D11/00—Solvent extraction
- B01D11/04—Solvent extraction of solutions which are liquid
- B01D11/0415—Solvent extraction of solutions which are liquid in combination with membranes
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
- G01N30/14—Preparation by elimination of some components
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/62—Detectors specially adapted therefor
- G01N30/72—Mass spectrometers
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
- G01N2030/062—Preparation extracting sample from raw material
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
- G01N30/14—Preparation by elimination of some components
- G01N2030/146—Preparation by elimination of some components using membranes
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- Chemical & Material Sciences (AREA)
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- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Chemical Kinetics & Catalysis (AREA)
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Abstract
The invention discloses a method for detecting contents of streptomycin and dihydrostreptomycin in honey, which comprises the following steps: (1) sample pretreatment: weighing a honey sample, adding water, mixing, then placing in a water bath at a certain temperature for dissolving, adding water for constant volume, and centrifuging; taking the supernatant of the sample, filtering the membrane type extraction device, adding water to wash the device, pumping air to enable the liquid to flow out completely, and discarding the effluent liquid; eluting with acetonitrile formate into a centrifuge tube, adding an aqueous solution of ammonia water, and mixing uniformly to obtain a sample; (2) preparation of standard solution: diluting with constant volume solution to obtain series of standard solutions with concentrations of 0, 0.25, 0.5, 1, 2, 4, and 8 μ g/L, detecting on a computer, and drawing a standard curve; (3) and (3) detection: and detecting by adopting a liquid chromatography-tandem mass spectrometry method. The determination method simplifies the operation flow of solid phase extraction, and simultaneously improves the accuracy, sensitivity and reproducibility of the method.
Description
Technical Field
The invention relates to the technical field of food and medicine detection, in particular to a method and a device for detecting contents of streptomycin and dihydrostreptomycin in honey.
Background
Honey is a good food therapy product, and can regulate physiological functions, eliminate fatigue, resist aging and assist in preventing and treating various diseases. With the health care function of honey accepted and accepted by more and more consumers, the consumption of honey is continuously increased, and people pursue the quality of honey products more and more. However, in recent years, the pesticide residues detected by honey products exceed the standard due to the fact that bee farmers abuse antibiotics and pesticides for preventing and treating bee and honeycomb diseases. Streptomycin and dihydrostreptomycin are common medicines, belong to aminoglycoside antibiotics, and have good curative effect on bee rotten son disease. However, streptomycin and dihydrostreptomycin can cause toxic and side effects such as anaphylactic shock, ototoxicity, nephrotoxicity and the like to human bodies, and therefore, the use of streptomycin and dihydrostreptomycin in the bee breeding process is prohibited in countries such as European Union, America and Japan. Therefore, in order to prevent beekeepers from illegally using streptomycin and dihydrostreptomycin, which results in the two drugs remaining in honey, it is necessary to establish an effective detection method.
At present, methods for detecting streptomycin and dihydrostreptomycin at home and abroad comprise a microbiological method, an enzyme-linked immunosorbent assay, a gas chromatography-mass spectrometry, a liquid chromatography-tandem mass spectrometry and the like. The liquid chromatography-tandem mass spectrometry is a more accurate and sensitive detection method, but streptomycin and dihydrostreptomycin have stronger polarity, so that a larger challenge is caused to the processing of a sample. The existing pretreatment methods usually need repeated extraction and purification by using different solid phase extraction columns, and some methods also need to use ions to carry out purification on heptafluoro-n-butyric acid and trifluoroacetic acid, so that the methods are complex to operate, high in cost, low in accuracy and possibly cause damage to instruments.
The information disclosed in this background section is only for enhancement of understanding of the general background of the invention and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.
Disclosure of Invention
The invention aims to provide a method for detecting contents of streptomycin and dihydrostreptomycin in honey, so that the defects of complex operation, high cost and low accuracy of the conventional detection method are overcome.
Another object of the present invention is to provide a sample pretreatment apparatus for measuring drug residues in food.
In order to achieve the aim, the invention provides a method for detecting the content of streptomycin and dihydrostreptomycin in honey, which comprises the following steps:
(1) sample pretreatment
Weighing a honey sample, adding water, mixing, then placing in a water bath at a certain temperature for dissolving, adding water to a constant volume, and centrifuging; taking supernatant of a sample, washing the device by adding water, pumping air to enable all liquid to flow out, and discarding the effluent liquid; eluting with acetonitrile formate to a centrifugal tube, adding an aqueous solution of ammonia water, and mixing uniformly to obtain a sample;
(2) preparation of Standard solutions
Weighing streptomycin and dihydrostreptomycin standard substances, dissolving the streptomycin and dihydrostreptomycin standard substances with water, fixing the volume to obtain standard stock solutions with a certain concentration, respectively transferring the streptomycin and dihydrostreptomycin standard stock solutions with the same dosage into a same volumetric flask, and adding water for dilution to obtain a mixed standard intermediate solution of streptomycin and dihydrostreptomycin;
taking the standard intermediate solution, diluting with constant volume solution (10% acetonitrile formate and 10% ammonia water solution mixed at a ratio of 1: 1) to obtain series standard solutions with concentrations of 0, 0.25, 0.5, 1, 2, 4 and 8 μ g/L, respectively detecting on a machine, and drawing a standard curve;
(3) detection
And (3) detecting the sample obtained in the step (1) and the standard solution prepared in the step (2) by using the same liquid chromatography-tandem mass spectrometry.
Preferably, in the above technical solution, the specific method for sample pretreatment in step (1) is: weighing 5g of honey sample, accurately weighing the sample to 0.01g, and placing the sample in a 50mL centrifuge tube; adding 20mL of water, and dissolving in a water bath at 40 ℃; adding water to a constant volume of 25mL, and centrifuging at 4000r/min for 5 min; taking 1mL of supernatant fluid to filter the membrane type extraction device, taking 1mL of water to wash the device, pumping air to enable all liquid to flow out, and discarding the effluent liquid; eluting 2mL of 10% acetonitrile formate to a 15mL centrifuge tube, and pumping air into the centrifuge tube to enable all liquid to flow out; adding 2mL of 10% aqueous solution of ammonia water, mixing by vortex, and bottling.
Preferably, in the above technical solution, the conditions of the liquid chromatography in step (3) are as follows: a chromatographic column: BEH Amind, 2.1X 100mm, 1.7 μm; temperature of the column: at 40 ℃; a mobile phase A: 0.5% formic acid water; mobile phase B: methanol; sample injection amount: 5 mu L of the solution; an elution mode: gradient elution.
Preferably, in the above technical solution, the gradient elution conditions are as follows:
| time (min) | Flow rate (mL/min) | Mobile phase A (%) | Mobile phase B (%) |
| 0 | 0.4 | 10 | 90 |
| 1.5 | 0.4 | 10 | 90 |
| 2.5 | 0.4 | 65 | 35 |
| 5.0 | 0.4 | 75 | 25 |
| 5.1 | 0.4 | 10 | 90 |
| 6 | 0.4 | 10 | 90 |
Preferably, in the above technical solution, the conditions of the mass spectrometry in step (3) are: an ion source: electrospray ion source (ESI), positive ion mode; the detection mode comprises the following steps: multiple Reaction Monitoring (MRM); mass spectrum parameters: air curtain gas (CUR): 30 psi; collision gas (CAD): medium; ion Source (IS): 4500V; temperature (TEM): 500 ℃; nebulization (GS 1): 55 psi; auxiliary heating gas (GS 2): 55 psi.
A filter membrane type extraction device is used for the determination method, and is used for detecting the contents of streptomycin and dihydrostreptomycin in honey, and the device comprises the following components: the base is provided with a through hole penetrating through the upper surface and the lower surface of the base, and the outer surface of the base is provided with threads; the flow guide assembly comprises an inner gland, an upper mounting plate and a first Ruhr joint, the inner gland is of a cavity structure, the lower edge of the cover body is bent outwards to form a bent part, the inner gland is detachably arranged on the base and is partially positioned in the base, the bent part is in clearance fit with the inner wall of the base, the upper mounting plate is arranged at the lower end of the inner gland, a plurality of water permeable holes are formed in the upper mounting plate, and the first Ruhr joint is positioned at the upper end of the inner gland and is communicated with the cavity of the inner gland; the sealing cover is provided with a through hole and is covered above the inner gland, the first Ruhr joint penetrates through the through hole of the sealing cover, a spring is arranged in the sealing cover, the upper end of the spring is arranged on the sealing cover, the lower end of the spring is in contact with the bent part of the inner gland, the inner wall of the sealing cover is provided with threads, and the sealing cover is connected to the base in a threaded manner; the filter element assembly comprises a filter element and at least one filter membrane, the filter element is arranged in the through hole of the base, the filter element is polytetrafluoroethylene filler modified by carboxyl, and the at least one filter membrane is positioned below the filter element; and the drainage tube is arranged on the base and is positioned below the filter element component.
Preferably, in the above technical solution, the outer surface of the base is provided with scales.
Preferably, in the above technical scheme, the number of the filter membranes is two, and the two filter membranes are respectively arranged above and below the filter element.
Preferably, among the above-mentioned technical scheme, base lower extreme detachable is equipped with down the mounting panel, be equipped with a plurality of holes of permeating water on the mounting panel down, the filter core is located on the mounting panel down.
Preferably, in the above technical solution, the spring is one, and is sleeved outside the inner gland, and the lower end of the spring is in contact with the bending portion of the inner gland, and the upper end of the spring is in contact with the inside of the upper end of the sealing cover.
Preferably, in the above technical solution, the number of the springs is plural, the plural springs are located between the lower surface of the cover and the bending portion of the inner gland, the upper end of each spring is fixed on the cover, and the lower end of each spring abuts against the bending portion.
Preferably, in the above technical scheme, the drainage tube is clamped on the base, and a second luer connector is arranged at the lower end of the drainage tube.
Compared with the prior art, the invention has the following beneficial effects:
(1) the method for detecting the contents of streptomycin and dihydrostreptomycin in honey simplifies the operation flow of solid phase extraction and improves the accuracy, sensitivity and reproducibility of the method by using the sample pretreatment method.
(2) According to the filter membrane type extraction device, the seal cover is arranged on the flow guide assembly, the spring is arranged between the seal cover and the flow guide assembly, the seal cover is in threaded connection with the base, the distance of the inner gland moving in the through hole of the base is adjusted by rotating the seal cover, and the extrusion degree of the upper mounting plate on the filter element can be adjusted. When the sample is processed, the shrinkage of the whole filter element in the drying process of the filter element can be compensated, and the phenomenon that the filter element cracks or breaks away from the base and the like is prevented so as to adapt to the elastic whole filter column. The problem of the shrinkage of the elastic integral filter element is overcome. The efficiency and the precision of detection are improved.
Drawings
FIG. 1 is a chromatogram of streptomycin in a spiked (10. mu.g/kg) sample according to the present invention;
FIG. 2 is a chromatogram of dihydrostreptomycin in a spiked (10. mu.g/kg) sample according to the invention;
FIG. 3 is a schematic diagram of the structure of a membrane type extraction apparatus according to the present invention;
FIG. 4 is a schematic structural diagram of another embodiment of the membrane type extraction apparatus of the present invention;
FIG. 5 is a schematic diagram of the structure of the upper mounting plate in the membrane type extraction device of the present invention.
Detailed Description
Specific embodiments of the present invention will be described in detail below with reference to the accompanying drawings, but it should be understood that the scope of the present invention is not limited to the specific embodiments.
Throughout the specification and claims, unless explicitly stated otherwise, the word "comprise", or variations such as "comprises" or "comprising", will be understood to imply the inclusion of a stated element or component but not the exclusion of any other element or component.
A method for detecting contents of streptomycin and dihydrostreptomycin in honey comprises the following steps:
(1) sample pretreatment
Weighing a honey sample, adding water, mixing, then placing in a water bath at a certain temperature for dissolving, adding water to a constant volume, and centrifuging; taking the supernatant of the sample, filtering the membrane type extraction device, adding water to wash the device, pumping air to enable the liquid to flow out completely, and discarding the effluent liquid; eluting with acetonitrile formate into a centrifuge tube, adding an aqueous solution of ammonia water, and mixing uniformly to obtain a sample;
(2) preparation of Standard solutions
Weighing streptomycin and dihydrostreptomycin standard substances, dissolving the streptomycin and dihydrostreptomycin standard substances with water, fixing the volume to obtain scales, preparing standard stock solutions with certain concentration, respectively transferring the streptomycin and dihydrostreptomycin standard stock solutions with the same dosage into the same volumetric flask, and adding water for dilution to prepare a mixed standard intermediate solution of the streptomycin and the dihydrostreptomycin;
taking the standard intermediate solution, diluting with constant volume solution (10% acetonitrile formate and 10% ammonia water solution mixed at a ratio of 1: 1) to obtain series standard solutions with concentrations of 0, 0.25, 0.5, 1, 2, 4 and 8 μ g/L, respectively detecting on a machine, and drawing a standard curve;
(3) detection of
And (3) respectively detecting the sample obtained in the step (1) and the standard solution prepared in the step (2) by adopting a liquid chromatography-tandem mass spectrometry method.
The filter membrane type extraction apparatus used for the pretreatment of the sample in the measurement method of the present invention can be treated by using a sample pretreatment purifier for measuring the residual amount of guanidine pesticide compounds in food, which is applied in patent ZL 202121914064.4 of the applicant. Or using the filter membrane type extraction device of the invention for treatment.
As shown in figures 3-5, the filter membrane type extraction device is used for detecting the contents of streptomycin and dihydrostreptomycin in honey by the measuring method. The filter membrane type extraction device comprises: the device comprises a base 1, a flow guide assembly 2, a sealing cover 3, a filter element assembly 4 and a drainage tube 5. The guide assembly 2 is arranged on the base 1, the sealing cover 3 is arranged on the guide assembly 2 and in threaded connection with the base 1, the filter element assembly 4 is located in a cavity of the base 1, and the drainage tube 5 is arranged on the base 1 and located below the base 1. The sample liquid is processed from the flow guide component 2, filtered by the filter element component 4 and flows out through the drainage tube 5.
The concrete structure is as follows: the base 1 is provided with a through hole 11 penetrating through the upper and lower surfaces thereof, and the outer surface of the base 1 is provided with an internal thread or an external thread, in this embodiment, an external thread 12. The flow guide assembly 2 comprises an inner gland 21, an upper mounting plate 22 and a first Ruhr joint 23, the inner gland 21 is provided with a cavity 24, the lower edge of the cover body of the inner gland 21 is bent outwards to form a bent part 25, and the bent part 25 is bent by 90 degrees. The inner gland 21 is detachably arranged on the base 1 and is partially positioned in the through hole of the base 1. The edge of the bending portion 222 is in clearance fit with the inner wall of the through hole 11 of the base. The upper mounting plate 22 is arranged at the lower end of the inner gland 21, and a plurality of water permeable holes 221 are arranged on the upper mounting plate 22. Preferably, the lower surface of the upper mounting plate 22 is provided with a plurality of ribs 222 arranged to cross each other. A first luer fitting 23 is provided at the upper end of the inner gland 21 and communicates with the cavity 24 of the inner gland. When sampling, sampling is carried out by using a syringe, the syringe is connected with the first luer connector 23, and sampling and filtering are carried out.
The sealing cover 3 is provided with a through hole 31, the first luer connector 23 penetrates through the through hole 31 of the sealing cover, and the sealing cover 3 is arranged above the inner gland 21 in a covering mode. A spring 6 is arranged in the sealing cover 3, the upper end of the spring 6 is arranged on the sealing cover 3, and the lower end of the spring is in contact with the bending part 24 of the inner gland. In this embodiment, the spring 6 is one, the spring 6 is sleeved outside the inner gland 21, the lower end of the spring is in contact with the bending part 24 of the inner gland, and the upper end of the spring is in contact with the inside of the upper end of the sealing cover 3. Preferably, the inner surface of the upper end of the cover 3 is provided with a spring groove 32, the upper end of the spring 6 is placed in the spring groove 32, and the spring 6 is limited by the spring groove 32 to prevent the spring 6 from deviating in the moving process. The inner wall of the side of the cover 3 is provided with an internal or external thread, in this embodiment an internal thread 33. The cover 3 is fixed on the base by the matching of the internal thread 33 and the external thread 12 on the base. By rotating the cover 3, the spring 6 biases the inner cover 21, and the position of the inner cover 21 in the base through hole 11 is adjusted.
Another embodiment of the spring arrangement is that a plurality of springs, 2 in this embodiment, namely springs 61 and 62, are arranged between the lower surface of the cover 3 and the bent part 24 of the inner gland, the spring 61 is located on the left side of the inner gland, and the spring 62 is located on the right side of the inner gland. The upper end of the spring is fixed on the cover 3, and the lower end of the spring abuts against the bent part 24. When the cover 3 is rotationally moved downward, the springs 61 and 62 apply a downward force to the inner pressing cover 21.
A filter element assembly 4 is arranged below the flow guide assembly 2, and the filter element assembly 4 comprises a filter element 41 and at least one filter membrane 42. The filter element is made of tetrafluoroethylene filler modified by carboxyl. The filter element 41 is arranged in the through hole 11 of the base, and at least one filter membrane 42 is arranged above or below the filter element 41. Preferably, the number of the filter membranes in this embodiment is 2, and the filter membranes are respectively arranged above and below the filter element 41. Base 1 lower extreme detachable is equipped with down mounting panel 26, is equipped with a plurality of holes of permeating water on the lower mounting panel 26, and lower mounting panel 26 upper surface is equipped with the strengthening rib of a plurality of intercrossing settings. The filter element 41 is arranged on the lower mounting plate 26, and a tetrafluoroethylene filter membrane is arranged between the filter element 41 and the lower mounting plate 26.
Because the surface of the polytetrafluoroethylene filter element 41 contains rich carboxyl after carboxyl modification, sample liquid passes through the filter membrane 42, large-particle substances are filtered, carboxyl-modified tetrafluoroethylene filler flows, streptomycin and dihydrostreptomycin in honey are rapidly combined with the carboxyl on the surface of the filter element, then an organic solvent with strong acidity, such as 10% acetonitrile formate, is used to be placed in the inner gland cavity 222, and the acidic organic solution can elute the streptomycin and dihydrostreptomycin in honey on the surface of the acidic organic solution when passing through the polytetrafluoroethylene filter element 1. The carboxyl modified tetrafluoroethylene filler can adsorb streptomycin and dihydrostreptomycin in honey as much as possible. The pretreatment of the sample is processed, so that the detection efficiency and precision are improved to a greater extent.
According to the filter membrane type extraction device, the seal cover is arranged on the flow guide assembly, the spring is arranged between the seal cover and the flow guide assembly, the seal cover is in threaded connection with the base, the distance of the inner gland moving in the through hole of the base is adjusted by rotating the seal cover, and the extrusion degree of the upper mounting plate on the filter element can be adjusted. When a sample is processed, the shrinkage of the whole filter core which removes the pore-forming agent and is used in the drying process of the filter core can be compensated, and the phenomena that the filter core cracks or breaks away from the base and the like are prevented so as to adapt to the elastic whole filter column. The problem of the shrinkage of the elastic integral filter element is solved. The efficiency and the precision of detection are improved.
Preferably, the outer surface of the base 1 is provided with scales, so that the rotation angle of the cover 3 can be accurately controlled.
Preferably, the drainage tube 5 is clamped on the base 1, the drainage tube 5 is funnel-shaped, and the lower end of the drainage tube is provided with a second luer connector 51.
1. Instruments, materials and reagents
1290Infinity II liquid chromatograph, Eclipse Plus C18 column (2.1X 100mm,1.8 μm) (Agilent, USA); qtrap 4500 mass spectrometer (AB SCIEX, USA); flying pigeon DL-5-B centrifuge (Shanghai' an pavilion scientific instrument factory); VOTEX GENIE2 vortex mixer (Scientific Industries, USA); GM200 knife mill (Retsch, germany); a special filter membrane type solid phase extraction device (patent number: ZL 202121914064.4).
Acetonitrile, methanol, dichloromethane, formic acid were chromatographically pure grades, available from Tedia, usa. Streptomycin sulfate standard substance, CAS number 3810-74-0, purity more than or equal to 90.3%; the dihydrostreptomycin sulfate standard substance with CAS number 5490-27-7 and purity more than or equal to 99.6 percent is purchased from Dr.Ehrenstontorfer, Germany, and is dissolved by using 0.3 percent acetic acid aqueous solution to prepare and convert the salt coefficient.
2. Test section
2.1 sample treatment
Weighing 5g of honey sample, accurately weighing the sample to 0.01g, and placing the sample in a 50mL polypropylene centrifuge tube; adding 20mL of water, and dissolving in a water bath at 40 ℃; adding water to a constant volume of 25mL, and centrifuging at 4000r/min for 5 min; 1mL of the supernatant was taken out by a syringe (1mL, without a needle) and passed through a dedicated filtration membrane device, 1mL of the supernatant was washed with water, air was introduced to completely discharge the liquid, and the discharge liquid was discarded. Then, 1 hydrophobic PTFE needle filter (common filter membrane) was attached, 2mL of 10% formic acid acetonitrile was eluted into a 15mL centrifuge tube with a syringe (2mL, no needle), and air was added to completely flow out the liquid. Adding 2mL of 10% aqueous ammonia solution, mixing by vortex, and bottling.
2.2 preparation of Standard solution
Weighing 10mg of streptomycin and dihydrostreptomycin standard substances, dissolving the streptomycin and dihydrostreptomycin standard substances with water, fixing the volume to obtain standard stock solutions with the concentration of 1mg/mL, respectively transferring 1.0mL of streptomycin and dihydrostreptomycin standard stock solutions into the same 100mL volumetric flask, and adding water for dilution to obtain a mixed standard intermediate solution with the concentrations of both streptomycin and dihydrostreptomycin of 10 mu g/mL.
2.3 Standard Curve preparation
Taking the standard intermediate solution, diluting the standard intermediate solution into a series of standard solutions with the concentrations of 0, 0.25, 0.5, 1, 2, 4 and 8 mu g/L by using a constant volume solution (10% acetonitrile formate and 10% ammonia water solution are mixed according to a ratio of 1: 1), detecting on a computer, and drawing a standard curve by taking the peak areas of streptomycin and dihydrostreptomycin as ordinate and the concentrations as abscissa respectively for quantification.
2.4 chromatographic and Mass Spectrometry conditions
A chromatographic column: BEH Amind, 2.1X 100mm, 1.7 μm; temperature of the column: 40 ℃; mobile phase A: 0.5% formic acid water; mobile phase B: methanol; gradient elution procedure: see table 1; sample introduction amount: 5 μ L.
TABLE 1 gradient elution procedure
An ion source: electrospray ion source (ESI), positive ion mode; the detection mode is as follows: multiple Reaction Monitoring (MRM); mass spectrum parameters: multiple Reaction Monitoring (MRM); mass spectrum parameters: air curtain gas (CUR): 30 psi; collision gas (CAD): a Medium; ion Source (IS): 4500V; temperature (TEM): 500 ℃; spray mist (GS 1): 55 psi; auxiliary heating gas (GS 2): 55 psi. . Streptomycin and dihydrostreptomycin mass spectrometry parameters, see table 2.
TABLE 2 ion Pair parameters
Quantification of ions
3. Results and discussion
3.1 matrix Effect
Matrix Effect (ME) refers to a phenomenon in which co-efflux components in a sample matrix affect ionization of a target compound during detection by an instrument, resulting in reduction or enhancement of a detection signal of the target compound. In the research, 7 parts of samples are weighed, pretreated and purified, streptomycin and dihydrostreptomycin standard solutions are added before bottling to enable the final concentrations to be 0, 0.25, 0.5, 1, 2, 4 and 8 mu g/L, then a series of standard solutions with the same concentration are prepared by using constant volume solutions, and after sample injection, a matrix curve and a solvent curve are fitted by respectively taking the concentration as an x axis and the peak area as a y axis. Then, the matrix effect ME ═ (B-a)/a × 100% (a is the slope of the linear equation of the solvent standard curve, and B is the slope of the linear equation of the matrix standard curve) was calculated. The results show that the purification effect of the method is good and the matrix effect is low, wherein the matrix effect ME of streptomycin is-6.4%, the matrix effect ME of dihydrostreptomycin is-9.1%, and the absolute values of the dihydrostreptomycin are less than 10%.
3.2 detection and quantitation limits
The detection limit and the quantification limit of the method are limited by the sensitivity of the instrument and are simultaneously influenced by the pretreatment process and the matrix effect of the sample. In the research, streptomycin and dihydrostreptomycin with low concentration levels are added into a negative honey sample for a labeling test, so that the minimum mass concentrations meeting the signal-to-noise ratio S/N of more than or equal to 3 and S/N of more than or equal to 10 are respectively determined as the detection limit and the quantification limit of the method. The detection limit of streptomycin and dihydrostreptomycin is 5 mug/kg, and the quantification limit is 10 mug/kg.
3.3 Linear Range, recovery and precision
In the invention, streptomycin standard solutions of 10, 20 and 50 mu g/kg and dihydrostreptomycin standard solutions are respectively added into a negative honey sample, 6 addition concentrations are set in parallel, and a standard recovery rate experiment is carried out.
Meanwhile, standard curves of 0, 0.25, 0.5, 1, 2, 4 and 8 mu g/L are prepared by using the constant volume solution for quantification.
The results are shown in Table 3, the linear correlation of streptomycin and dihydrostreptomycin is good in the linear range of 0.25-8 mug/L, and the correlation coefficients r are respectively 0.9975 and 0.9971; the standard recovery range of streptomycin at low, medium and high 3 concentration levels is 86.5% -105.5%, and the relative standard deviation is 2.2% -5.7%; the standard recovery rate range of the dihydrostreptomycin at low, medium and high 3 concentration levels is 87.8-114.5%, and the relative standard deviation is 5.4-5.9%. The chromatograms obtained for the labeled sample are shown in FIGS. 1 and 2, in which FIG. 1 is a chromatogram for streptomycin in a labeled (10. mu.g/kg) sample according to the present invention; FIG. 2 is a chromatogram of dihydrostreptomycin in a spiked (10. mu.g/kg) sample according to the invention.
TABLE 3 linear equation of the spiking test, recovery and precision
The foregoing description of specific exemplary embodiments of the invention has been presented for the purposes of illustration and description. It is not intended to limit the invention to the precise form disclosed, and obviously many modifications and variations are possible in light of the above teaching. The exemplary embodiments were chosen and described in order to explain certain principles of the invention and its practical application to enable one skilled in the art to make and use various exemplary embodiments of the invention and various alternatives and modifications as are suited to the particular use contemplated. It is intended that the scope of the invention be defined by the claims and their equivalents.
Claims (10)
1. A method for detecting the content of streptomycin and dihydrostreptomycin in honey is characterized by comprising the following steps:
(1) sample pretreatment
Weighing a honey sample, adding water, mixing, then placing in a water bath at a certain temperature for dissolving, adding water for constant volume, and centrifuging; taking the supernatant of the sample, filtering the membrane type extraction device, adding water to wash the device, pumping air to enable the liquid to completely flow out, and removing the effluent liquid; eluting with acetonitrile formate to a centrifugal tube, adding an aqueous solution of ammonia water, and mixing uniformly to obtain a sample;
(2) preparation of Standard solution
Weighing streptomycin and dihydrostreptomycin standard substances, dissolving the streptomycin and dihydrostreptomycin standard substances with water, fixing the volume to obtain scales, preparing standard stock solutions with certain concentration, respectively transferring the streptomycin and dihydrostreptomycin standard stock solutions with the same dosage into the same volumetric flask, and adding water for dilution to prepare a mixed standard intermediate solution of the streptomycin and the dihydrostreptomycin;
taking the standard intermediate solution, diluting the constant volume solution into series standard solutions with the concentrations of 0, 0.25, 0.5, 1, 2, 4 and 8 mu g/L respectively, and performing machine detection respectively to draw a standard curve;
(3) detection of
And (3) detecting the sample obtained in the step (1) and the standard solution prepared in the step (2) by using the same liquid chromatography-tandem mass spectrometry method.
2. The method for detecting content of streptomycin and dihydrostreptomycin in honey as claimed in claim 1, wherein the sample pretreatment in step (1) comprises the following specific steps: weighing 5g of honey sample, accurately weighing the honey sample to 0.01g, and placing the honey sample in a 50mL centrifuge tube; adding 20mL of water, and dissolving in a water bath at 40 ℃; adding water to a constant volume of 25mL, and centrifuging at 4000r/min for 5 min; taking 1mL of supernatant fluid to filter the membrane type extraction device, taking 1mL of water to wash the device, pumping air into the device to enable all liquid to flow out, and discarding the effluent liquid; eluting 2mL of 10% acetonitrile formate to a 15mL centrifuge tube, and pumping air into the centrifuge tube to enable all liquid to flow out; adding 2mL of 10% aqueous ammonia solution, mixing by vortex, and bottling.
3. The method for detecting the content of streptomycin and dihydrostreptomycin in honey as claimed in claim 1, wherein the conditions of the liquid chromatography in the step (3) are as follows: and (3) chromatographic column: BEH Amind, 2.1X 100mm, 1.7 μm; temperature of the column: 40 ℃; a mobile phase A: 0.5% formic acid water; mobile phase B: methanol; sample introduction amount: 5 mu L of the solution; and (3) an elution mode: and (4) gradient elution.
4. The method for detecting content of streptomycin and dihydrostreptomycin in honey as claimed in claim 3, wherein the gradient elution condition is:
5. The method for detecting content of streptomycin and dihydrostreptomycin in honey as claimed in claim 1, wherein the mass spectrometry in step (3) is carried out under the following conditions: an ion source: electrospray ion source (ESI), positive ion mode; the detection mode comprises the following steps: multiple Reaction Monitoring (MRM); mass spectrum parameters: air curtain gas (CUR): 30 psi; collision gas (CAD): a Medium; ion Source (IS): 4500V; temperature (TEM): 500 ℃; spray mist (GS 1): 55 psi; auxiliary heating gas (GS 2): 55 psi.
6. A filter membrane type extraction device for detecting contents of streptomycin and dihydrostreptomycin in honey by using the determination method of claim 1, comprising:
the base is provided with a through hole penetrating through the upper surface and the lower surface of the base, and the outer surface of the base is provided with threads;
the flow guide assembly comprises an inner gland, an upper mounting plate and a first Ruhr joint, the inner gland is of a cavity structure, the lower edge of the cover body is bent outwards to form a bent part, the inner gland is detachably arranged on the base and is partially positioned in the base, the bent part is in clearance fit with the inner wall of the base, the upper mounting plate is arranged at the lower end of the inner gland, a plurality of water permeable holes are formed in the upper mounting plate, and the first Ruhr joint is positioned at the upper end of the inner gland and is communicated with the cavity of the inner gland;
the sealing cover is provided with a through hole and is covered above the inner gland, the first Ruhr joint penetrates through the through hole of the sealing cover, a spring is arranged in the sealing cover, the upper end of the spring is arranged on the sealing cover, the lower end of the spring is contacted with the bent part of the inner gland, the inner wall of the sealing cover is provided with threads, and the sealing cover is connected to the base in a threaded manner;
the filter element assembly comprises a filter element and at least one filter membrane, the filter element is arranged in the through hole of the base, the filter element is polytetrafluoroethylene filler modified by carboxyl, and the at least one filter membrane is positioned below the filter element; and
and the drainage tube is arranged on the base and positioned below the filter element assembly.
7. The membrane extraction device according to claim 6, wherein the outer surface of the base is provided with a scale.
8. The membrane filtration extraction apparatus according to claim 6, wherein the number of the filtration membranes is two, and the two filtration membranes are respectively arranged above and below the filtration core.
9. The filtration membrane extraction device according to claim 6, wherein the lower end of the base is detachably provided with a lower mounting plate, the lower mounting plate is provided with a plurality of water permeable holes, and the filter element is arranged on the lower mounting plate.
10. The membrane type extraction device according to claim 6, wherein the spring is one, the spring is sleeved outside the inner gland, the lower end of the spring is in contact with the bent part of the inner gland, and the upper end of the spring is in contact with the inner part of the upper end of the sealing cover; or
The spring is a plurality of, a plurality of the spring is located the closing cap lower surface to between the kink of interior gland, every the spring upper end is fixed on the closing cap, the lower extreme butt is in kink department.
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| CN113373077A (en) * | 2021-02-07 | 2021-09-10 | 南宁海关技术中心 | High-efficiency chloramphenicol degrading bacterium, high-efficiency degrading microbial inoculum and application thereof |
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