CN105771308A - Efficient method for extracting sulfonamide residues in animal derived food - Google Patents
Efficient method for extracting sulfonamide residues in animal derived food Download PDFInfo
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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- G—PHYSICS
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- 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
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- G—PHYSICS
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- 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
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- G01N2030/062—Preparation extracting sample from raw material
Abstract
The invention belongs to the technical field of sample pretreatment in analytical chemistry, and relates to an efficient method for extracting sulfonamide residues in animal derived food. The efficient method includes synthesizing a sulfonic polystyrene high-molecular polymer, preparing a nanofiber membrane from the sulfonic polystyrene high-molecular polymer through electrostatic spinning, and treating the surface of the nanofiber membrane with plasmas. The high-hydrophilia and high-stability sulfonic functional group nanofiber membrane is prepared, and a sample pretreatment method for effectively enriching sulfonamide type veterinary drug residues without degreasing steps is created. By the sulfo group modified hydrophilia nanofiber membrane, efficient enrichment, extraction and analysis of the sulfonamide type veterinary drug residues of 13 types of labeled samples and market samples in the animal derived food can be realized. By the method, the sulfonamide residues in fat-rich animal derived food base materials can be enriched selectively, utilization of normal hexane is not needed, operation steps are reduced, emulsification is avoided, and accordingly, extraction efficiency is improved remarkably; the method has the advantages of rapidness, simplicity, convenience, high efficiency and high repeatability.
Description
Technical field
The present invention provides a kind of and efficiently extracts the sample pretreating method of sulfa drug residue in animal derived food based on sulfonic group high-hydrophilic functionalized nano-fiber film, belongs to Sample Pretreatment Technique Used field in analytical chemistry.
Background technology
Veterinary drug preventing and treating Animal diseases, improve production efficiency, improve Animal product quality etc. in play a very important role.But, abuse veterinary drug very easily causes the residual of harmful substance in animal-derived food, and health is not only caused direct harm by this, and the development and ecological environment to animal husbandry also results in high risks.Along with people to animal-derived food by demand type to the transformation of mass type, the residue of veterinary drug in animal-derived food has been increasingly becoming the important focus of food-safety problem.Sulfa drugs (SAs) is one of important drugs being now widely used for poultry anti-infective therapy, has stable in properties, has a broad antifungal spectrum, is easy to store, use the advantages such as simple, low price.But at nearly 15～20 years, in the animal-derived food such as pig, fowl, cattle, the residual quantity of sulfonamide phenomenon that exceeds standard was extremely serious, and countries in the world all have corresponding laws and regulations to limit the standard of Sulfonamides residual.China also promulgated new regulation in 2013 and starts it is supervised (GB29694-2013 " in animal food the mensuration of 13 kinds of sulphonamides multi-relicts ").
Sulfonamides compound (SAs) is the antimicrobial drug of a class synthetic, the history of existing decades on veterinary clinic, its mother nucleus structure has sulfoamido and virtue primary amino radical, and wherein sulfoamido has faintly acid, virtue primary amino radical has alkalescence, and therefore sulfanilamide has soda acid both sexes.Hydrogen atom on sulfoamido can be replaced by different heterocyclic substituents, forms various sulfonamide.Sulfa drugs is almost insoluble in water, is soluble in methanol, ethanol, acetone, acetonitrile, chloroform and dichloromethane polar organic solvent, is insoluble in non-polar organic solvent.But, owing to sulfa drugs has soda acid both sexes, by regulating the pH of solution, it is possible to making sulfa drugs is different conditions, i.e. neutral molecule or ionic molecule, thus changing the partition coefficient of aqueous phase and organic facies.
Solid-Phase Extraction (SolidPhaseExtraction is called for short SPE) is the major sample pretreatment technology of animal-derived food veterinary drug residue, in the national standard method issued and implemented in recent years, has a lot of means using Solid-Phase Extraction as sample pre-treatments.Current GB29694-2013 " in animal food the mensuration of 13 kinds of sulphonamides multi-relicts " adopts MCX (Mixed-modeCationeXchange) solid phase extraction column that the Sulfonamides in animal derived food is remained and is enriched with and purifies.The principle of reaction is under suitable pH, and the azochlorosulfonate acid anion on Solid-Phase Extraction material with sulfonamides compound, reversible ion-exchange reactions can occur, thus selectivity catches this compounds, reaches the purpose of Selective Separation and enrichment.But existing sample pre-treatments step is still loaded down with trivial details, and due in animal derived food substrate rich in fat, often need to adopt normal hexane defat, very easily there is emulsion in this step so that the response rate of sample is on the low side.
Electrospun nano-fibers (abbreviation electrostatic spinning nano fiber) is a kind of method polymer solution or melt being carried out spinning by high-pressure electrostatic effect, utilizes the method can simply and quickly prepare diameter range high molecular polymer nanofiber between 10～1000nm.Electrospun nano-fibers has the advantages such as specific surface area is big, be prone to film forming, permeability is good, and have multiple macromolecule polymer material available, binding film surface treatment and modification technique, it is expected to obtain high performance functionalized nano-fiber film, meets the requirement of heterogeneity compound selective enrichment.
Summary of the invention
In order to overcome drawbacks described above, the invention provides and efficiently extract the method for sulfa drug residue in animal derived food based on sulfonic group high-hydrophilic functionalized nano-fiber film.Sulfa drugs has both sexes, and available sulfonate ion occurs ion-exchange reactions to reach the purpose of selective enrichment in acid condition with it.During the Solid-Phase Extraction material (MCX) that additionally existing national standard method specifies sulfa drug residue in the rich aliphatic radical matter of enrichment, operating procedure is complicated; and remain a need for by normal hexane defat; this step often causes sample liquid emulsifying, loses sample segment information.The benzenesulfonic acid polystyrene polymeric polymer of synthesis is prepared into nano fibrous membrane by Static Spinning technology by the present invention, and using plasma irradiation technique, film surface treatment is become hydrophilic, establish without adopt normal hexane fat removal step can the high-performance sulfonic group hydrophilic fibrous membrane of sulfonamides compound in selective enrichment richness aliphatic radical matter, the sample pre-treatments fields such as Sulfonamides residual that are expected to be applied in the animal derived food of selective enrichment richness fat.
In order to realize foregoing invention purpose, the technical solution adopted in the present invention is: a kind of method of sulfa drug residue in efficient extraction animal derived food, it is characterised in that comprise the steps of
1) synthesis of sulfonic group polystyrene polymeric polymer: styrene monomer, 4-vinylbenzenesulfonic acid sodium and sodium carbonate are placed in triangle reaction bulb, add ultra-pure water, magneton stirring adds persulfate initiator and continues magneton stirring reaction after reaching polymeric reaction temperature to solution；Polyreaction stops stirring after terminating, organic naphtenic acid is added after milky suspension is cooled to room temperature, fully place a period of time after mixing, centrifugal sedimentation, discards the supernatant, takes lower sediment and inserts beaker, put into after washing in vacuum drying oven and dry, grind to form powdery, repeat washing-drying-grinding steps, to obtain final product；
2) prepared by high polymer nanometer fiber membrane: by step 1) high molecular polymer that synthesizes is dissolved in organic solvent, it is configured to certain density polymer solution, cathode collector aluminium foil is placed circular lid slide, prepares nano fibrous membrane by electrostatic spinning technique；
3) Cement Composite Treated by Plasma nano fibrous membrane surface: by step 2) nano fibrous membrane prepared is placed in plasma generator, treatment with irradiation under some strength, obtains the sulfonic group nano fibrous membrane of surface hydrophilicity；
4) animal derived food sample preparation: take homogeneous animal derived food and be placed in centrifuge tube, accurately weighed, add sulfonamides Quality Control medicine, after addition ethyl acetate after shaking table concussion, low-temperature centrifugation, Aspirate supernatant, residue repeats to extract once by ethyl acetate again；Merging supernatant, water-bath nitrogen dries up, and adds Na2EDTA solution, vortex mixed obtains sample solution；
5) SPE sample purification and extraction: step 3) the hydrophilic sulfonic acid groups nano fibrous membrane prepared is placed in commercially available detachable filter, respectively with methanol and Na2After the activation of EDTA solution, by step 4) sample solution prepared by fibrous membrane, uses Na with constant speed afterwards2EDTA solution drip washing fibrous membrane；Adding the target compound containing the absorption of organic acid methanol solution eluting, eluent water-bath nitrogen dries up, with liquid-phase chromatographic analysis mobile phase constant volume.
Step 1) described in reaction raw materials styrene monomer, 4-vinylbenzenesulfonic acid sodium, sodium carbonate, ultra-pure water, persulfate and organic acid consumption respectively be 2～10mL, 0.5～1.5g, 0.10～0.60g, 10～40mL, 0.10～0.30g and 1～4mL；Persulfate is one or more in Ammonium persulfate., sodium peroxydisulfate, potassium peroxydisulfate；Organic acid is the one in formic acid, acetic acid；Step 1) described in polymeric reaction temperature maintain 50～80 DEG C, polymerization reaction time is 12～24h；The rotating speed of centrifugal sedimentation is at 12000～20000r/min, and the sedimentation time controls at 30～40min, and washing-baking step repeats 2-4 time, and vacuum drying temperature is set in 50～60 DEG C.
Step 2) described in organic solvent be oxolane (THF), N,N-dimethylformamide (DMF), hexafluoroisopropanol (HFP), chloroform (CH3Cl) one or several；Polymer solution concentration is the mass/volume percentage ratio that polymer quality accounts for organic solvent volume, and its scope is 8～20%；Circular lid slide specification is commercially available diameter 14mm coverslip；Electrospinning conditions is voltage 10～30kV, and spinning receiving range 10～20cm, polymer solution flow controls at 0.5～1.0mL/h.
Step 3) described in the exposure rate of plasma generator be 10～30W, the time is 10～60s.
nullStep 4) described in sulfa drugs include sulfacetamide (SA，CAS6209-17-2)、Sulfapyridine (SP，CAS144-83-2)、Sulfamethyldiazine (SM1，CAS127-79-7)、Sulfanilamide azoles (SX，CAS729-99-7)、Sulfamethazine (SM2，CAS57-68-1)、Sulfamethoxypyridazine (SMP，CAS80-35-3)、Sulfamonomethoxine (SMM，CAS38006-08-5)、Cistosulfa (SCP，CAS80-32-0)、Sulfamethoxazole (SMZ，CAS723-46-6)、Ganda (SIZ，CAS127-69-5)、Sulfabenzamide (SML，CAS127-71-9)、Sulfadimethoxine (SDM，And sulfaphenazole (SPP CAS122-11-2)，CAS526-08-9) one or several in，Its concentration range 50～200 μ g/kg.
Step 4) and step 5) described in Na2Concentration 0.010～0.030mol/L, the pH3 of EDTA solution～5；Water-bath nitrogen dries up temperature and controls at 50～70 DEG C.
Step 4) described in shaking table shake 20～30min with rotating speed 200～300r/min, be centrifuged 3～7min at low temperature 3～5 DEG C and 8000～12000r/min rotating speed.
Step 5) described in detachable filter refer to the detachable filter that commercial polypropylene (PP) material, specification are 13mm diameter, the loading speed of sample solution is 0.5～1.5mL/min；Organic acid in methanol solution is the one in formic acid, acetic acid, and its concentration 0.1% accounts for methanol solution (referring to pure methanol) volume ratio for organic acid volume, and its consumption is 2.0～3.0mL；Liquid-phase chromatographic analysis mobile phase constant volume is 1.0～2.0mL.
Relative to national standard method (GB29694-2013 " in animal food the mensuration of 13 kinds of sulphonamides multi-relicts "), what the present invention set up efficiently extract the method for sulfa drug residue in animal derived food based on sulfonic group high-hydrophilic functionalized nano-fiber film has a characteristic that
Prepared sulfonic group polystyrene nano fiber membrane stability flushing good, resistance to, it is possible in acid condition with 13 kinds of typical sulfa drugs generation ion-exchange reactionss, the Sulfonamides residual in selective enrichment animal derived food substrate.
There is the characteristic of soda acid both sexes according to sulfa drugs, by controlling extraction solution acidity scope (pH3～5), utilize azochlorosulfonate acid anion on Solid-Phase Extraction material with sulfonamides compound, the principle of reversible ion-exchange reactions can occur, selectivity catches this compounds, reaches the purpose of efficiently concentrating and purification.
Adopt sulfonic group polystyrene polymeric Polymer process simplicity, reaction temperature and and polymer yield height prepared by emulsion polymerization.
With the nano fibrous membrane prepared by Electrospun nano-fibers, there is high-specific surface area；Processed by Plasma-Modified, make film surface be transferred to hydrophily by hydrophobic state, improve the Solid-Phase Extraction effect of rich aliphatic radical matter intermediate ion state sulfa drugs.Prepare nano fibrous membrane and plasma irradiating technology by electrostatic spinning technique the process of membrane surface modification is simple and easy to do, be suitable for producing in enormous quantities.
The supporting circular lid slide diameter of commercial standard 24 well culture plate (diameter is 15.6mm) is 14mm, therefore the nano fibrous membrane diameter prepared on this circular lid slide by electrostatic spinning technique is also 14mm, just can be positioned in the split type liquid filter of commercially available diameter 13mmPP material, it is simple to the later stage, applying nano fibrous membrane was as selective enrichment material.Selected enrichment defecator is simple and easy to get, the later stage is easy to use, matching is good.
The method need not adopt normal hexane defat, decreases operating procedure, it is to avoid emulsion, thus significantly improving recovery of extraction, has quick, easy, efficient, reproducible feature.
Accompanying drawing explanation
Fig. 1 is field emission scanning electron microscope (FE-SEM) figure of the sulfonic group hydrophilic polystyrene nano fiber film prepared by embodiment 1；
Fig. 2 is Fourier transformation-infrared spectrum (FT-IR) figure of the sulfonic group hydrophilic polystyrene nano fiber film prepared by embodiment 1；
Fig. 3 is water contact angle (WaterContactAngle) figure of the sulfonic group hydrophilic polystyrene nano fiber film prepared by embodiment 1；
Fig. 4 more different Solid-Phase Extraction (SPE) material (the polystyrene plasma-PS nano fibrous membrane of Cement Composite Treated by Plasma, polystyrene PS nano fibrous membrane and the MCX pillar) response rate result (each sulfa drugs addition is 100 μ g/kg) in Carnis Sus domestica 13 kinds of sulfa drug residues.
Detailed description of the invention
By the examples below the present invention is further described.
Embodiment 1 (in Carnis Sus domestica sample 13 kinds of sulfonamide retention analysiss)
1) synthesis of sulfonic group polystyrene polymeric polymer: 5.0mL styrene monomer, the 4-vinylbenzenesulfonic acid sodium of 1.0g and 0.30g sodium carbonate are placed in triangle reaction bulb, add 20mL ultra-pure water, in 65 DEG C of magneton stirring reaction 10min, add 0.20g ammonium persulfate initiator, continue 65 DEG C of magneton stirring reaction 12h.Reaction stops stirring after terminating, milky suspension is cooled to room temperature, adds 2mL formic acid breakdown of emulsion, fully place a period of time after mixing, centrifugal sedimentation (16000r/min, 30min), discard the supernatant, take lower sediment and insert beaker, 55 DEG C of drying in vacuum drying oven are put into after washing, grind to form powdery, repeat above-mentioned washing-drying-grinding steps 2 times, to obtain final product.
2) prepared by high polymer nanometer fiber membrane: by step 1) the sulfonic group polystyrene polymeric polymer that synthesizes is dissolved in THF:DMF (1/3, v/v) in organic solvent, it is configured to the polymer solution that concentration is 15%, adopt electrostatic spinning technique, the cathode collector aluminium foil of spinning receiving range 15cm is placed diameter 14mm circular lid slide, applying 15kV voltage, polymer solution flow controls at 0.7mL/h, and nano fibrous membrane is prepared in collection.
3) Cement Composite Treated by Plasma nano fibrous membrane surface: by step 2) nano fibrous membrane prepared is placed in plasma generator, and under 30W intensity, irradiate 40s, obtain the nano fibrous membrane of surface hydrophilicity.
null4) preparation of sulfonamide mark-on sample in blank Carnis Sus domestica sample: take 5.00 ± 0.05g and be placed in 50mL centrifuge tube without the Sulfonamides homogeneous Carnis Sus domestica of residual，Accurately weighed，Add sulfacetamide、Sulfapyridine、Sulfamethyldiazine、Sulfanilamide azoles、Sulfamethazine、Sulfamethoxypyridazine、Sulfamonomethoxine、Cistosulfa、Sulfamethoxazole、Ganda、Sulfabenzamide、Sulfadimethoxine and sulfaphenazole reference substance mixed solution 25～100 μ L，Prepare into containing the above-mentioned each sulfonamides substrate concentration serial mark-on sample solution 50～200 μ g/kg (referring to the mass concentration of every kind of sulfa drugs quality/homogeneous pork quality)，Add 10mL ethyl acetate，After shaking table concussion 20min (300r/min)，10000r/min is centrifuged 5min (4 DEG C)，Aspirate supernatant，Residue repeats to extract once by 10mL ethyl acetate again.Merge supernatant, dry up in 60 DEG C of water-bath nitrogen, add the Na of the 0.020mol/L of 2.5mL2EDTA solution (pH4), vortex mixed 1min.
5) preparation of Marketing pork sample: take the commercially available homogeneous Carnis Sus domestica to be detected of 5.00 ± 0.05g and be placed in 50mL centrifuge tube, accurately weighed, after after adding 10mL ethyl acetate, shaking table shakes 20min (300r/min), 10000r/min is centrifuged 5min (4 DEG C), Aspirate supernatant, residue repeats to extract once by 10mL ethyl acetate again.Merge supernatant, dry up in 60 DEG C of water-bath nitrogen, add the Na of the 0.020mol/L of 2.5mL2EDTA solution (pH4), vortex mixed 1min.
6) SPE sample purification and extraction: by step 3) the hydrophilic sulfonic acid groups nano fibrous membrane prepared is placed in the PP detachable filter of commercially available 13mm diameter, respectively with the Na of 1.0mL methanol and 1.0mL2After EDTA solution (0.020mol/L, pH4) activated fiber film, by step 4) and 5) the serial mark-on solution prepared and each 2mL of testing sample solution iterate through solid-phase extraction column with the constant speed of 0.7mL/min, afterwards with the Na of 2.0mL2EDTA solution (0.020mol/L, pH4) drip washing solid-phase extraction column.Add 2.5mL methanol (containing 0.1% formic acid, v/v) target compound of eluting absorption, eluent dries up in 60 DEG C of water-bath nitrogen, with the liquid-phase chromatographic analysis mobile phase (aqueous formic acid of 0.1%: acetonitrile=90/10, v/v) it is settled to 1.0mL, to obtain final product.
7) according to step 4) the serial mark-on solution the prepared data fitting standard curve (see table 1) by obtaining after Solid-Phase Extraction, liquid-phase chromatographic analysis, by step 5) Liquid Chromatography data that obtains contrasts with standard curve, obtains step 5) kind of the sulfa drug residue of actual Marketing pork sample prepared and residual quantity thereof.
Material (plasma-PSSA) prepared in embodiment 1 and solid phase extraction method and common polystyrene (PS) nano fibrous membrane and national regulations method (MCX pillar) etc. being contrasted, result is shown in Fig. 4.Undertaken contrasting (table 2) by embodiment 1 acquired results and literature procedure simultaneously.Visible by above-mentioned contrast, the sulfa drug residue in the Carnis Sus domestica of high fat content is had and is enriched with clean-up effect preferably by the method, and method is quick, easy.
Linear, the response rate (high, medium and low) measurement result of 13 kinds of sulfa drug residues (SAs) in the blank Carnis Sus domestica sample of table 1
The mensuration of sulfa drug residue and document comparative result in table 2 Carnis Sus domestica
Note: [1] GambaV, TerzanoC, FioroniL, MorettiS, DusiG, GalariniR.Developmentandvalidationofaconfirmatorymethodf orthedeterminationofsulphonamidesinmilkbyliquidchromatog raphywithdiodearraydetection.Analyticachimicaacta.2009；637(1-2):18-23.
[2]KishidaK,FurusawaN.Matrixsolid-phasedispersionextractionandhigh-performanceliquidchromatographicdeterminationofresidualsulfonamidesinchicken,JournalofchromatographyA,2001；937:49-55.
[3]FangGZ,HeJX,WangS.Multiwalledcarbonnanotubesassorbentforon-linecouplingofsolid-phaseextractiontohigh-performanceliquidchromatographyforsimultaneousdeterminationof10sulfonamidesineggsandpork.JournalofchromatographyA.2006；1127(1-2):12-7.
[4]GaoR,ZhangJ,HeX,ChenL,ZhangY.Selectiveextractionofsulfonamidesfromfoodbyuseofsilica-coatedmolecularlyimprintedpolymernanospheres.AnalyticalandBioanalyticalChemistry.2010；398(1):451-61.
[5]HeJ,TangH,YouL,ZhanH,ZhuJ,LuK.Fragment-imprintedmicrospheresfortheextractionofsulfonamides.MicrochimicaActa.2013；180(9-10):903-10.
[6]KarimiM,AboufazeliF,ZhadHRLZ,SadeghiO,NajafiE.DeterminationofSulfonamidesinChickenMeatbyMagneticMolecularlyImprintedPolymerCoupledtoHPLC-UV.FoodAnalyticalMethods.2014；7(1):73-80.
Embodiment 2 (in chicken meat sample 13 kinds of sulfonamide retention analysiss)
1) synthesis of sulfonic group polystyrene polymeric polymer: 2.5mL styrene monomer, the 4-vinylbenzenesulfonic acid sodium of 0.5g and 0.15g sodium carbonate are placed in triangle reaction bulb, add 10mL ultra-pure water, in 75 DEG C of magneton stirring reaction 10min, add 0.20g sodium peroxydisulfate initiator, continue 75 DEG C of magneton stirring reaction 24h.Reaction stops stirring after terminating, milky suspension is cooled to room temperature, adds 1mL acetic acid breakdown of emulsion, fully place a period of time after mixing, centrifugal sedimentation (14000r/min, 30min), discard the supernatant, take lower sediment and insert beaker, 60 DEG C of drying in vacuum drying oven are put into after washing, grind to form powdery, repeat above-mentioned washing-drying-grinding steps 2 times, to obtain final product.
2) prepared by high polymer nanometer fiber membrane: by step 1) the sulfonic group polystyrene polymeric polymer that synthesizes is dissolved in THF:DMF (2/2, v/v) in organic solvent, it is configured to the polymer solution that concentration is 12%, adopt electrostatic spinning technique, the cathode collector aluminium foil of spinning receiving range 15cm is placed diameter 14mm circular lid slide, applying 12kV voltage, polymer solution flow controls at 0.8mL/h, and nano fibrous membrane is prepared in collection.
3) Cement Composite Treated by Plasma nano fibrous membrane surface: by step 2) nano fibrous membrane prepared is placed in plasma generator, and under 30W intensity, irradiate 40s, obtain the nano fibrous membrane of surface hydrophilicity.
null4) preparation of sulfonamide mark-on sample in blank chicken meat sample: take 5.00 ± 0.05g and be placed in 50mL centrifuge tube without the Sulfonamides homogeneous Carnis Gallus domesticus of residual，Accurately weighed，Add sulfacetamide、Sulfapyridine、Sulfamethyldiazine、Sulfanilamide azoles、Sulfamethazine、Sulfamethoxypyridazine、Sulfamonomethoxine、Cistosulfa、Sulfamethoxazole、Ganda、Sulfabenzamide、Sulfadimethoxine and sulfaphenazole reference substance mixed solution 25～100 μ L，Prepare into the serial mark-on sample solution containing above-mentioned each sulfa drugs 50～200 μ g/kg (referring to the mass concentration of every kind of sulfa drugs quality/homogeneous Carnis Gallus domesticus quality)，Add 10mL ethyl acetate，After shaking table concussion 20min (300r/min)，10000r/min is centrifuged 5min (4 DEG C)，Aspirate supernatant，Residue repeats to extract once by 10mL ethyl acetate again.Merge supernatant, dry up in 60 DEG C of water-bath nitrogen, add the Na of the 0.010mol/L of 2.5mL2EDTA solution (pH3.5), vortex mixed 1min.
5) preparation of commercially available chicken meat sample: take the commercially available Carnis Gallus domesticus to be detected of 5.00 ± 0.05g and be placed in 50mL centrifuge tube, accurately weighed, after after adding 10mL ethyl acetate, shaking table shakes 20min (300r/min), 10000r/min is centrifuged 5min (4 DEG C), Aspirate supernatant, residue repeats to extract once by 10mL ethyl acetate again.Merge supernatant, dry up in 60 DEG C of water-bath nitrogen, add the Na of the 0.010mol/L of 2.0mL2EDTA solution (pH3.5), vortex mixed 1min.
6) SPE sample purification and extraction: by step 3) the hydrophilic sulfonic acid groups nano fibrous membrane prepared is placed in the PP detachable filter of commercially available 13mm diameter, respectively with the Na of 1.0mL methanol and 1.0mL2EDTA solution (0.010mol/L, pH3.5) after activated fiber film, by step 4) and 5) the serial mark-on solution prepared and each 2mL of testing sample solution iterate through solid-phase extraction column with the constant speed of 0.6mL/min, afterwards with the Na of 2.0mL2EDTA solution (0.010mol/L, pH3.5) drip washing solid-phase extraction column.Add 2.5mL methanol (containing 0.1% formic acid, v/v) target compound of eluting absorption, eluent dries up in 60 DEG C of water-bath nitrogen, with the liquid-phase chromatographic analysis mobile phase (aqueous formic acid of 0.1%: acetonitrile=90/10, v/v) it is settled to 2.0mL, to obtain final product.
7) according to step 4) the serial mark-on solution the prepared data fitting standard curve by obtaining after Solid-Phase Extraction, liquid-phase chromatographic analysis, by step 5) Liquid Chromatography data that obtains contrasts with standard curve, obtains step 5) kind of sulfa drug residue in the commercially available chicken meat sample of reality prepared and its residual quantity thereof.
Embodiment 3 (in beef sample 13 kinds of sulfonamide retention analysiss)
1) synthesis of sulfonic group polystyrene polymeric polymer: 5.0mL styrene monomer, the 4-vinylbenzenesulfonic acid sodium of 1.0g and 0.30g sodium carbonate are placed in triangle reaction bulb, add 20mL ultra-pure water, in 65 DEG C of magneton stirring reaction 10min, add 0.20g ammonium persulfate initiator, continue 65 DEG C of magneton stirring reaction 12h.Reaction stops stirring after terminating, milky suspension is cooled to room temperature, adds 2mL formic acid breakdown of emulsion, fully place a period of time after mixing, centrifugal sedimentation (18000r/min, 30min), discard the supernatant, take lower sediment and insert beaker, 55 DEG C of drying in vacuum drying oven are put into after washing, grind to form powdery, repeat above-mentioned washing-drying-grinding steps 2 times, to obtain final product.
2) prepared by high polymer nanometer fiber membrane: by step 1) the sulfonic group polystyrene polymeric polymer that synthesizes is dissolved in THF:DMF (1/3, v/v) in organic solvent, it is configured to the polymer solution that concentration is 15%, adopt electrostatic spinning technique, the cathode collector aluminium foil of spinning receiving range 15cm is placed diameter 14mm circular lid slide, applying 15kV voltage, polymer solution flow controls at 0.7mL/h, and nano fibrous membrane is prepared in collection.
3) Cement Composite Treated by Plasma nano fibrous membrane surface: by step 2) nano fibrous membrane prepared is placed in plasma generator, and under 30W intensity, irradiate 50s, obtain the nano fibrous membrane of surface hydrophilicity.
null4) preparation of sulfonamide mark-on sample in blank beef sample: take 5.00 ± 0.05g and be placed in 50mL centrifuge tube without the Sulfonamides homogeneous beef of residual，Accurately weighed，Add sulfacetamide、Sulfapyridine、Sulfamethyldiazine、Sulfanilamide azoles、Sulfamethazine、Sulfamethoxypyridazine、Sulfamonomethoxine、Cistosulfa、Sulfamethoxazole、Ganda、Sulfabenzamide、Sulfadimethoxine and sulfaphenazole reference substance mixed solution 25～100 μ L，Prepare into the serial mark-on sample solution containing above-mentioned each sulfa drugs 50～200 μ g/kg (referring to the mass concentration of every kind of sulfa drugs quality/homogeneous Quality Beef)，Add 10mL ethyl acetate，After shaking table concussion 20min (300r/min)，10000r/min is centrifuged 5min (4 DEG C)，Aspirate supernatant，Residue repeats to extract once by 10mL ethyl acetate again.Merge supernatant, dry up in 60 DEG C of water-bath nitrogen, add the Na of the 0.020mol/L of 2.5mL2EDTA solution (pH4.5), vortex mixed 1min.
5) preparation of commercially available beef sample: take the commercially available homogeneous beef to be detected of 5.00 ± 0.05g and be placed in 50mL centrifuge tube, accurately weighed, after after adding 10mL ethyl acetate, shaking table shakes 20min (300r/min), 8000r/min is centrifuged 5min (4 DEG C), Aspirate supernatant, residue repeats to extract once by 10mL ethyl acetate again.Merge supernatant, dry up in 60 DEG C of water-bath nitrogen, add the Na of the 0.020mol/L of 2.5mL2EDTA solution (pH4.5), vortex mixed 1min.
6) SPE sample purification and extraction: by step 3) the hydrophilic sulfonic acid groups nano fibrous membrane prepared is placed in the PP detachable filter of commercially available 13mm diameter, respectively with the Na of 1.0mL methanol and 1.0mL2EDTA solution (0.020mol/L, pH4.5) after activated fiber film, by step 4) and 5) the serial mark-on solution prepared and each 2mL of testing sample solution iterate through solid-phase extraction column with the constant speed of 0.7mL/min, afterwards with the Na of 2.0mL2EDTA solution (0.020mol/L, pH4.5) drip washing solid-phase extraction column.Add 2.0mL methanol (containing 0.1% formic acid, v/v) target compound of eluting absorption, eluent dries up in 60 DEG C of water-bath nitrogen, with the liquid-phase chromatographic analysis mobile phase (aqueous formic acid of 0.1%: acetonitrile=90/10, v/v) it is settled to 1.0mL, to obtain final product.
7) according to step 4) the serial mark-on solution the prepared data fitting standard curve by obtaining after Solid-Phase Extraction, liquid-phase chromatographic analysis, by step 5) Liquid Chromatography data that obtains contrasts with standard curve, obtains step 5) kind of the sulfa drug residue of the commercially available beef sample of reality prepared and residual quantity thereof.
Embodiment 4 (in milk sample 13 kinds of sulfonamide retention analysiss)
1) synthesis of sulfonic group polystyrene polymeric polymer: 10.0mL styrene monomer, the 4-vinylbenzenesulfonic acid sodium of 2.0g and 0.60g sodium carbonate are placed in triangle reaction bulb, add 40mL ultra-pure water, in 65 DEG C of magneton stirring reaction 10min, add 0.20g ammonium persulfate initiator, continue 65 DEG C of magneton stirring reaction 12h.Reaction stops stirring after terminating, milky suspension is cooled to room temperature, adds 4mL acetic acid breakdown of emulsion, fully place a period of time after mixing, centrifugal sedimentation (18000r/min, 30min), discard the supernatant, take lower sediment and insert beaker, 60 DEG C of drying in vacuum drying oven are put into after washing, grind to form powdery, repeat above-mentioned washing-drying-grinding steps 2 times, to obtain final product.
2) prepared by high polymer nanometer fiber membrane: by step 1) the sulfonic group polystyrene polymeric polymer that synthesizes is dissolved in THF:DMF (1/3, v/v) in organic solvent, it is configured to the polymer solution that concentration is 10%, adopt electrostatic spinning technique, the cathode collector aluminium foil of spinning receiving range 10cm is placed diameter 14mm circular lid slide, applying 10kV voltage, polymer solution flow controls at 0.7mL/h, and nano fibrous membrane is prepared in collection.
3) Cement Composite Treated by Plasma nano fibrous membrane surface: by step 2) nano fibrous membrane prepared is placed in plasma generator, and under 30W intensity, irradiate 30s, obtain the nano fibrous membrane of surface hydrophilicity.
null4) preparation of sulfonamide mark-on sample in blank milk sample: take 5.00 ± 0.05g and be placed in 50mL centrifuge tube without the milk that Sulfonamides remains，Accurately weighed，Add sulfacetamide、Sulfapyridine、Sulfamethyldiazine、Sulfanilamide azoles、Sulfamethazine、Sulfamethoxypyridazine、Sulfamonomethoxine、Cistosulfa、Sulfamethoxazole、Ganda、Sulfabenzamide、Sulfadimethoxine and sulfaphenazole reference substance mixed solution 25～100 μ L，Prepare into the serial mark-on sample solution containing above-mentioned each sulfa drugs 50～200 μ g/kg (referring to the mass concentration of every kind of sulfa drugs quality/milk quality)，Add 10mL ethyl acetate，After shaking table concussion 20min (300r/min)，10000r/min is centrifuged 5min (4 DEG C)，Aspirate supernatant，Residue repeats to extract once by 10mL ethyl acetate again.Merge supernatant, dry up in 60 DEG C of water-bath nitrogen, add the Na of the 0.020mol/L of 2.0mL2EDTA solution (pH4), vortex mixed 1min.
5) preparation of commercially available milk sample: take the commercially available milk to be detected of 5.00 ± 0.05g and be placed in 50mL centrifuge tube, accurately weighed, after after adding 10mL ethyl acetate, shaking table shakes 20min (300r/min), 10000r/min is centrifuged 5min (4 DEG C), Aspirate supernatant, residue repeats to extract once by 10mL ethyl acetate again.Merge supernatant, dry up in 60 DEG C of water-bath nitrogen, add the Na of the 0.020mol/L of 2.5mL2EDTA solution (pH4), vortex mixed 1min.
6) SPE sample purification and extraction: by step 3) the hydrophilic sulfonic acid groups nano fibrous membrane prepared is placed in the PP detachable filter of commercially available 13mm diameter, respectively with the Na of 1.0mL methanol and 1.0mL2After EDTA solution (0.020mol/L, pH4) activated fiber film, by step 4) and 5) the serial mark-on solution prepared and each 2mL of testing sample solution iterate through solid-phase extraction column with the constant speed of 0.7mL/min, afterwards with the Na of 2.0mL2EDTA solution (0.020mol/L, pH4) drip washing solid-phase extraction column.Add 2.5mL methanol (containing 0.1% formic acid, v/v) target compound of eluting absorption, eluent dries up in 60 DEG C of water-bath nitrogen, with the liquid-phase chromatographic analysis mobile phase (aqueous formic acid of 0.1%: acetonitrile=90/10, v/v) it is settled to 1.0mL, to obtain final product.
7) according to step 4) the serial mark-on solution the prepared data fitting standard curve by obtaining after Solid-Phase Extraction, liquid-phase chromatographic analysis, by step 5) Liquid Chromatography data that obtains contrasts with standard curve, obtains step 5) kind of the sulfa drug residue of the commercially available milk sample of reality prepared and residual quantity thereof.
The above is only the preferred embodiment of the present invention; it is noted that, for those skilled in the art; under the premise without departing from the principles of the invention; can also making the replacement of some improvement and equivalents, these improve and the equivalent technical scheme obtained of replacing also should belong to protection scope of the present invention.
Claims (8)
1. the method for sulfa drug residue in an efficient extraction animal derived food, it is characterised in that comprise the steps of
1) synthesis of sulfonic group polystyrene polymeric polymer: styrene monomer, 4-vinylbenzenesulfonic acid sodium and sodium carbonate are placed in triangle reaction bulb, add ultra-pure water, magneton stirring adds persulfate initiator and continues magneton stirring reaction after reaching polymeric reaction temperature to solution；Polyreaction stops stirring after terminating, organic naphtenic acid is added after milky suspension is cooled to room temperature, fully place a period of time after mixing, centrifugal sedimentation, discards the supernatant, takes lower sediment and inserts beaker, put into after washing in vacuum drying oven and dry, grind to form powdery, repeat washing-drying-grinding steps, to obtain final product；
2) prepared by high polymer nanometer fiber membrane: is dissolved in organic solvent by the high molecular polymer that step 1) synthesizes, is configured to certain density polymer solution, places circular lid slide, prepare nano fibrous membrane by electrostatic spinning technique on cathode collector aluminium foil；
3) Cement Composite Treated by Plasma nano fibrous membrane surface: by step 2) nano fibrous membrane prepared is placed in plasma generator, treatment with irradiation under some strength, obtains the sulfonic group nano fibrous membrane of surface hydrophilicity；
4) animal derived food sample preparation: take homogeneous animal derived food and be placed in centrifuge tube, accurately weighed, add sulfonamides Quality Control medicine, after addition ethyl acetate after shaking table concussion, low-temperature centrifugation, Aspirate supernatant, residue repeats to extract once by ethyl acetate again；Merging supernatant, water-bath nitrogen dries up, and adds Na2EDTA solution, vortex mixed obtains sample solution；
5) SPE sample purification and extraction: hydrophilic sulfonic acid groups nano fibrous membrane step 3) prepared is placed in commercially available detachable filter, respectively with methanol and Na2After the activation of EDTA solution, sample solution step 4) prepared by fibrous membrane, uses Na with constant speed afterwards2EDTA solution drip washing fibrous membrane；Adding the target compound containing the absorption of organic acid methanol solution eluting, eluent water-bath nitrogen dries up, with liquid-phase chromatographic analysis mobile phase constant volume.
2. the method for sulfa drug residue in a kind of efficient extraction animal derived food according to claim 1, it is characterized in that, reaction raw materials styrene monomer described in step 1), 4-vinylbenzenesulfonic acid sodium, sodium carbonate, ultra-pure water, persulfate and organic acid consumption respectively are 2 ~ 10mL, 0.5 ~ 1.5g, 0.10 ~ 0.60g, 10 ~ 40mL, 0.10 ~ 0.30g and 1 ~ 4mL；Persulfate is one or more in Ammonium persulfate., sodium peroxydisulfate, potassium peroxydisulfate；Organic acid is the one in formic acid, acetic acid；Polymeric reaction temperature described in step 1) maintains 50 ~ 80 DEG C, and polymerization reaction time is 12 ~ 24h；The rotating speed of centrifugal sedimentation is at 12000 ~ 20000r/min, and the sedimentation time controls at 30 ~ 40min, repeats washing-drying-grinding steps 2-4 time, and vacuum drying temperature is set in 50 ~ 60 DEG C.
3. the method for sulfa drug residue in a kind of efficient extraction animal derived food according to claim 1, it is characterized in that, step 2) described in organic solvent be oxolane (THF), DMF (DMF), hexafluoroisopropanol (HFP), chloroform (CH3Cl) one or several；Polymer solution concentration is the mass/volume percentage ratio that polymer quality accounts for organic solvent volume, and its scope is 8 ~ 20%；Circular lid slide specification is commercially available diameter 14mm coverslip；Electrospinning conditions is voltage 10 ~ 30kV, and spinning receiving range 10 ~ 20cm, polymer solution flow controls at 0.5 ~ 1.0mL/h.
4. the method for sulfa drug residue in a kind of efficient extraction animal derived food according to claim 1, it is characterised in that the exposure rate of the plasma generator described in step 3) is 10 ~ 30W, and the time is 10 ~ 60s.
null5. the method for sulfa drug residue in a kind of efficient extraction animal derived food according to claim 1，It is characterized in that，Sulfa drugs described in step 4) includes sulfacetamide (SA，CAS6209-17-2)、Sulfapyridine (SP，CAS144-83-2)、Sulfamethyldiazine (SM1，CAS127-79-7)、Sulfanilamide azoles (SX，CAS729-99-7)、Sulfamethazine (SM2，CAS57-68-1)、Sulfamethoxypyridazine (SMP，CAS80-35-3)、Sulfamonomethoxine (SMM，CAS38006-08-5)、Cistosulfa (SCP，CAS80-32-0)、Sulfamethoxazole (SMZ，CAS723-46-6)、Ganda (SIZ，CAS127-69-5)、Sulfabenzamide (SML，CAS127-71-9)、Sulfadimethoxine (SDM，And sulfaphenazole (SPP CAS122-11-2)，CAS526-08-9) one or several in，Its concentration range 50 ~ 200 μ g/kg.
6. the method for sulfa drug residue in a kind of efficient extraction animal derived food according to claim 1, it is characterised in that step 4) and the Na described in step 5)2Concentration 0.010 ~ 0.030mol/L, the pH3 of EDTA solution ~ 5；Water-bath nitrogen dries up temperature and controls at 50 ~ 70 DEG C.
7. the method for sulfa drug residue in a kind of efficient extraction animal derived food according to claim 1, it is characterized in that, shaking table described in step 4) shakes 20 ~ 30min with rotating speed 200 ~ 300r/min, at the centrifugal 3 ~ 7min of low temperature 3 ~ 5 DEG C and 8000 ~ 12000r/min rotating speed.
8. the method for sulfa drug residue in a kind of efficient extraction animal derived food according to claim 1, it is characterized in that, detachable filter described in step 5) refers to the detachable filter that commercial polypropylene (PP) material, specification are 13mm diameter, and the loading speed of sample solution is 0.5 ~ 1.5mL/min；Organic acid in eluting methanol solution is the one in formic acid, acetic acid, and its concentration 0.1% accounts for methanol solution volume ratio for organic acid volume, and its consumption is 2.0 ~ 3.0mL；Liquid-phase chromatographic analysis mobile phase constant volume is 1.0 ~ 2.0mL.
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