CN109738551A - A kind of method of imidaclothiz content in detection livestock meat - Google Patents
A kind of method of imidaclothiz content in detection livestock meat Download PDFInfo
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- CN109738551A CN109738551A CN201910147403.1A CN201910147403A CN109738551A CN 109738551 A CN109738551 A CN 109738551A CN 201910147403 A CN201910147403 A CN 201910147403A CN 109738551 A CN109738551 A CN 109738551A
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- 238000001514 detection method Methods 0.000 title claims abstract description 57
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- 244000144977 poultry Species 0.000 claims abstract description 5
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- MTXSIJUGVMTTMU-JTQLQIEISA-N (S)-anabasine Chemical compound N1CCCC[C@H]1C1=CC=CN=C1 MTXSIJUGVMTTMU-JTQLQIEISA-N 0.000 description 1
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- WACQKHWOTAEEFS-UHFFFAOYSA-N cyclohexane;ethyl acetate Chemical compound CCOC(C)=O.C1CCCCC1 WACQKHWOTAEEFS-UHFFFAOYSA-N 0.000 description 1
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- YWTYJOPNNQFBPC-UHFFFAOYSA-N imidacloprid Chemical compound [O-][N+](=O)\N=C1/NCCN1CC1=CC=C(Cl)N=C1 YWTYJOPNNQFBPC-UHFFFAOYSA-N 0.000 description 1
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- ZQEIXNIJLIKNTD-UHFFFAOYSA-N methyl N-(2,6-dimethylphenyl)-N-(methoxyacetyl)alaninate Chemical compound COCC(=O)N(C(C)C(=O)OC)C1=C(C)C=CC=C1C ZQEIXNIJLIKNTD-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
- Investigating Or Analysing Biological Materials (AREA)
Abstract
The present invention relates to a kind of methods of imidaclothiz content in detection livestock meat, belong to technical field of food detection.Present invention optimizes sample to be tested pre-treating method and liquid chromatograies, Mass Spectrometry Conditions, and the defect of livestock meat imidaclothiz medicament residue cannot be measured by solving existing method.The method of the present invention linear relationship within the scope of 10-400ng/mL is good, and detection is limited to 5.0 μ g/kg, and the method rate of recovery is 91.41%-93.51% in different livestock and poultry sarcenchymas, and relative standard deviation is between 2.4%-3.2%.The present invention has the characteristics of easy to operate, analysis speed is fast, high sensitivity, favorable reproducibility.It is significant to the quantitative detection of imidaclothiz medicament residue in the livestock meat of field of food detection.
Description
Technical field
The present invention relates to the detection methods of imidaclothiz medicament residue in livestock meat, belong to technical field of food detection.
Background technique
Imidaclothiz is a kind of anabasine insecticide, is after organic phosphorus, organochlorine, carbamate and pyrethroid
New pesticide after insecticide.Imidaclothiz insecticidal spectrum is wide, has prevention and treatment effect well to coleoptera, Diptera and lepidoptera pest
Fruit especially has relatively high virulence to leafhopper, planthopper, thrips, the snout moth's larva of rice.And because its is cheap, so that more and more
Plant personnel substitute original pesticide using imidaclothiz and carry out pest control.If not scientific in pesticide release link operation, often
It is exceeded to will cause pesticide in crops.Downstream of the livestock and poultry as food chain, eats the production of the crops such as corn, dregs of beans, chaff, wheat bran
The pesticide of product or byproduct, Use out of range can be run up in domestic animal body, finally jeopardize human health.
Imidaclothiz is provided most in GB 2763-2016 " national food safety standard Pesticide Residues maximum limitation "
Big maximum permission quantity is 0.1mg/kg in paddy, is 0.2mg/kg in wheat.Since imidaclothiz is a kind of new pesticide, institute
Corresponding examination criteria is promulgated not yet with the country.
Currently, the research about imidaclothiz detection method mainly has liquid chromatography[1], gas chromatography mass spectrometry method[2], colloidal gold exempts from
Epidemic disease chromatography[3], capillary electrophoresis[4]。
Liquid chromatography: method with Ethyl acetate-cyclohexane (V:V=1:1) be Extraction solvent, with ultrasonic extraction method water
Imidaclothiz in fruit, through Solid phase extraction, using liquid chromatography for measuring.Liquid chromatogram UV detector Detection wavelength is
230nm, mobile phase are acetonitrile-water (volume ratio 60: 40), flow 0.8ml/min, 20 μ l of sample volume.As a result imidaclothiz is linear
Range is 1.0 × 10-3-1.0×10-1μg/mL(R2=0.9998), average recovery rate 97.98%-100.43%, detection limit
It is 3.43 × 10-2Mg/kg, RSD 2.87%.This method can be used as the detection of imidaclothiz content in fruit.
Gas chromatography mass spectrometry method: method is purified with acetonitrile ultrasonic extraction, through Polymer Trap SPE, uses gas chromatography-mass spectrum
Qualitative and quantitative detection is carried out to imidaclothiz, pesticide is in good linear relationship within the scope of 0.1-10mg/kg mass concentration, related
Coefficient is R2=0.9989.Addition 0.05,0.2, the average recovery rate of 3 concentration of 1.0mg/kg are 83.1%- in rice
101.4%, relative standard deviation 1.3%-8.9%, minimal detectable concentration 0.05mg/kg, this method can be used in rice
The detection of imidaclothiz content.
Colloidal gold immunity chromatography: method utilizes the high affinity interaction of biotin-Streptavidin, by imidaclothiz antibody and
Strepto- parent and 41nm colloid gold label are prepared for the enhancing of imidaclothiz colloidal gold by biotinylation DNA and 13nm colloidal gold double labelling
Immuno-chromatographic test paper strip.In optimal conditions, test strips can realize visualization interpretation in 10min, and detection limit (LOD) is
2.5mg/kg, in addition to having larger cross reaction with imidacloprid, with other similar compound no cross reactions.This method can be used for chlorine
Detection of the thiophene quinoline in rice, cucumber, tomato, pears, wild cabbage and apple sample.
Capillary electrophoresis: micellar electrokinetic chromatography (MEKC) is combined to scan skill using dispersion liquid-liquid micro-extraction (DLLME)
Art establishes a kind of analysis method that imidaclothiz insecticide is detected in cucumber sample.With optimal conditions, concentration coefficient reaches
4000 to 10000.The range of linearity of this method is 2.7-200mg/kg, related coefficient (R2=0.9968).Detection is limited to
0.8mg/kg.Relative standard deviation when imidaclothiz insecticide concentration level is 10.0mg/kg in cucumber sample is 6.3%.It should
Method can be used for the analysis of imidaclothiz insecticide in cucumber.
Above method research object is the plant-derived samples such as water fruits and vegetables, tealeaves, rice, is had no in related livestock meat
The document report of imidaclothiz method for detecting residue.Since the pre-treating method of plant-derived sample is not suitable for containing compared with high protein
The fresh meat sample of matter and fat, above method are not particularly suited for imidaclothiz residue detection in livestock meat.In addition, above method is most
Low detection limits: liquid chromatography 3.43 × 10-2Mg/kg, gas chromatography mass spectrometry method 0.05mg/kg, colloidal gold immunity chromatography 2.5mg/
Kg, capillary electrophoresis 0.8mg/kg are unable to satisfy the demand of trace level medicament residue.
In order to detect the intracorporal imidaclothiz content of livestock and poultry, high performance liquid chromatography mass spectrometry is utilized the present invention provides a kind of
The method for detecting imidaclothiz residual quantity in livestock meat.
Bibliography:
[1] Gao Zhixi, Wu Yanhong, Ao Kehou, Xu Zhongxuan, Mu Qingsong, the solid phase of metalaxyl and imidaclothiz in Huang Cheng's fruit
Extraction-rp-hplc method [J] environment and health magazine .2012,36 (03): 258-259.
[2] Xu Xiuying, Shi Haiyan, Wang Minghua gas chromatography-mass spectrography measure 6 kinds of nicotine pesticide residues in rice
[J] mass spectrum journal, 2012,50 (2): 99-103.
[3] Shi Haiyan, Sheng Enze, Ma Ming, foundation [J] points for waiting imidaclothiz colloidal gold enhancing immunochromatographiassays assays method
Analysis chemistry, 2017,30 (3): 403-408.
[4]ZhANG S H,YANG X M,YIN X F,WANG C,WANG Z.Dispersive liquid–liquid
microextraction combined with sweeping micellar electrokinetic chromatography
for the determination of some neonicotinoid insecticides in cucumber samples
[J].Food Chemistry.2012,133(02):544-550.
Summary of the invention
For the detection method for establishing a kind of imidaclothiz medicament residue suitable for livestock meat, the present invention utilizes efficient liquid phase
Chromatographic tandem mass-spectrometric technique is detected, and can rapidly and accurately be measured the residual content of imidaclothiz in livestock meat, be compensated for it
The defect of his detection method in detection range, applicability or detection efficiency.This method is easy to operate, quick, and the rate of recovery is high, sensitive
Degree is high, method detection limit 0.0005mg/kg, has filled up blank for food safety detection technology.
Oil content and Protein content is high in livestock meat, and conventional method uses acetonitrile for solvent extraction imidaclothiz, institute in matrix
The various fatty acid and amino acid contained can be dissolved into extracting solution together in the form of molecular state, be brought to detection a large amount of dry
It disturbs, influences the accuracy of testing result.
The research of the invention finds that using acetonitrile and formic acid for Extraction solvent, while adding appropriate sodium chloride and anhydrous slufuric acid
Sodium fully can sufficiently extract livestock meat imidaclothiz, and efficiently avoid the fatty acid and amino of molecular state
The interference of acid, to improve the accuracy of testing result.
Specifically, the present invention is acetonitrile, formic acid, sodium chloride and anhydrous sulphur to extraction reagent used in sample to be tested pre-treatment
Sour sodium；Wherein, the volume ratio of acetonitrile and formic acid is 10:0.1；In terms of ml/g, the volume weight of acetonitrile and sodium chloride, anhydrous sodium sulfate
Amount is than being respectively 10:1 and 10:4.
For general livestock and poultry meat sample, in terms of ml/g, the volume weight of acetonitrile and sample to be tested in said extracted reagent
Ratio is measured with 10:(1-4) it is advisable, it is preferred especially with 10:2.
In addition, being to accelerate extraction rate and sufficiently extract imidaclothiz, the present invention is preferably first homogenized sample to be tested
Processing, is then extracted with mentioned reagent again.
Although the above method can substantially completely extract imidaclothiz in sample, inevitably also contain
Impurity and other uncertain chaff interferents such as a small amount of inositol, carnosine, nucleotide, therefore also need at further progress purification
Reason.
Due to sample difference, the impurity, chaff interferent in gained extracting solution are also different.The study found that existing conventional purification side
Method is not able to satisfy detection needs.Said extracted liquid is purified for example, by using solid phase extraction method, can not detect imidaclothiz.
The present invention is on the basis of many experiments it was unexpectedly observed that said extracted liquid is used PSA adsorbent (N- propyl second
Diamines) and C18 (carbon 18) adsorbent carry out adsorption cleaning can fully remove impurity and chaff interferent.Both adsorbents tool
There are certain collaboration or complementation.Wherein, the weight ratio of PSA adsorbent and C18 adsorbent is preferred with 1:3.
Specifically, to meet the needs that liquid chromatography tandem mass spectrometry detects imidaclothiz content in livestock meat, to test sample
Product pre-treating method is as follows:
After sample to be tested homogenate, 2.00g sample (being accurate to 0.01g) is accurately weighed in 50mL centrifuge tube, is added
10mL acetonitrile, 0.1mL formic acid, 1.00g sodium chloride, 4.00g anhydrous sodium sulfate；Vortex oscillation extract 1min, at 10 DEG C, in
5000r/min is centrifuged 5min；
Transfer upper organic phase is to being equipped in the 25mL centrifuge tube of 50mg PSA adsorbent and 150mg C18 adsorbent；Whirlpool
Whirlpool vibrates 1min, is centrifuged 5min at 10 DEG C, in 5000r/min；
Supernatant is shifted, nitrogen is blown to dry；It is redissolved with the acetonitrile solution of 1.00mL 50%, through 0.22 μm of miillpore filter mistake
After filter, as test sample liquid, for liquid chromatography tandem mass spectroscopy.
Liquid-phase condition optimization
The prior art mostly uses isocratic elution for the analysis measurement of imidaclothiz raw medicine ingredient, in C18 chromatographic column, diuril
Quinoline belongs to the compound retained more by force.Since protein in livestock meat and fat content are high, and because of fatty acids, amino
The impurity such as acid, inositol, carnosine, nucleotide are easy to interfere the analysis of target compound.
For this purpose, the present invention has attempted a variety of liquid phase chromatogram conditions.The present invention is selected on the basis of numerous studies using stream
Dynamic phase: A phase, acetonitrile；B phase, 0.1% aqueous formic acid；And separating effect is further increased using the method for gradient elution, it reduces
Impurity interference in matrix, and matrix effect when can reduce mass ions to the greatest extent.
Specific condition of gradient elution is as follows:
| Time/minute | Mobile phase A/% | Mobile phase B/% |
| 0-1.0 | 5 | 95 |
| 1.0-4.0 | 5-95 | 95-5 |
| 4.0-5.0 | 95 | 5 |
| 5.0-5.1 | 95-5 | 5-95 |
| 5.1-8.0 | 5 | 95 |
Other chromatographic conditions: use C18 chromatographic column, 35 DEG C of column temperature, flow velocity 0.30mL/min, 10 μ L of sample volume.
Mass Spectrometry Conditions optimization
For the accuracy for improving testing result, the mass spectrometry parameters that the present invention optimizes are as follows:
Mass spectrum uses electric spray ion source cation scan pattern (ESI+), and detection mode is more reaction detection modes
(MRM), ion source temperature is 550 DEG C, and electron spray voltage is 5500V, atomization gas pressure 0.050MPa, auxiliary heating atmospheric pressure
0.050MPa, gas curtain atmospheric pressure 0.015MPa.
The present invention carries out quantitative analysis using calibration curve method.
Calibration curve production method:
Identical with sample to be tested matrix anima is first selected, weighs 5 parts, every part of 2.00g, then by the chlorine of 50ng/mL
Thiophene quinoline standard working solution is respectively with 20 μ L, 40 μ L, and 100 μ L, 200 μ L, the volume of 400 μ L are added in anima component, press
It is handled according to method identical with sample to be tested pre-treatment, this 5 parts of solution is then implanted sequentially liquid chromatograph mass spectrography
In instrument, corresponding peak area is measured, it is 1.0ng/mL, 2.0ng/mL that corresponding concentration, which is calculated, in the additive amount according to imidaclothiz,
The standard series of 5.0ng/mL, 10ng/mL, 20ng/mL, peak area is corresponding with concentration, it is calculated, is obtained using least square method
Imidaclothiz matrix adds calibration curve.
As a result it calculates
Sample to be tested in gained test sample liquid injection liquid chromatograph-mass spectrometer, is measured corresponding after pre-treatment
Peak area, the concentration of imidaclothiz in test sample liquid is obtained by standard curve, further (1) is calculated to test sample as the following formula
Imidaclothiz content in product.
X=C × V/m ... ... ... ... ... (1)
In formula (1):
X --- the content of imidaclothiz in sample to be tested, unit are ng/kg or micro- gram per liter (μ g/kg)；
C --- the concentration of imidaclothiz in resulting test sample liquid is calculated by standard curve, unit is nanograms per milliliter
(ng/mL)；
V --- the final constant volume of test sample liquid, unit milliliter (mL)；
M --- sample to be tested weight, unit of gram (g)；
It is finally calculated by calculation formula, the residual content of imidaclothiz in sample.
The method of the present invention is suitable for the domestic animals and chicken, duck, goose, dove, quail etc. such as pig, ox, sheep, horse, camel, rabbit, dog
The detection of imidaclothiz in poultry meat.
The utility model has the advantages that
The present invention establishes the LC-MS detection method of imidaclothiz medicament residue in livestock meat, solves existing method not
The defect of livestock meat imidaclothiz medicament residue can be measured.The method of the present invention linear relationship within the scope of 10-400ng/mL is good, inspection
Rising limit is 5.0 μ g/kg, and the method rate of recovery is 91.41%-93.51% in different livestock and poultry sarcenchymas, and relative standard deviation exists
Between 2.4%-3.2%.The present invention has the characteristics of easy to operate, analysis speed is fast, high sensitivity, favorable reproducibility.To food
The quantitative detection of imidaclothiz medicament residue is significant in the livestock meat of detection field.
Detailed description of the invention
Fig. 1 imidaclothiz characteristic ion mass chromatogram.
In Fig. 2 embodiment 1 in pork matrix imidaclothiz mass chromatogram.
In Fig. 3 embodiment 2 in beef matrix imidaclothiz mass chromatogram.
In Fig. 4 embodiment 3 in mutton matrix imidaclothiz mass chromatogram.
In Fig. 5 embodiment 4 in chicken matrix imidaclothiz mass chromatogram.
The imidaclothiz mass chromatogram of solid phase extraction in Fig. 6 comparative example 1.
The imidaclothiz mass chromatogram of gas chromatography mass spectrometry method in Fig. 7 comparative example 2.
Mass chromatogram corresponding to chromatographic condition 1 in Fig. 8 experimental example 3.
Mass chromatogram corresponding to chromatographic condition 2 in Fig. 9 experimental example 3.
Specific embodiment
The following examples are used to illustrate the present invention, but are not intended to limit the scope of the present invention..It is not specified in embodiment specific
Technology or conditions person, described technology or conditions according to the literature in the art, or carried out according to product description.It is used
Production firm person is not specified in reagent or instrument, is the conventional products that can be commercially available by regular distributor.
Unless specifically indicated, instrument and reagent used below:
Key instrument: liquid chromatography tandem level four bars mass spectrometer, charged spray ion source, WATERS UPLC I-
CLASS XEVO TQ
Main agents:
Imidaclothiz standard items (purity >=96%)；
Acetonitrile (chromatographically pure)；
Formic acid (chromatographically pure)；
Sodium chloride (analysis is pure)；
Anhydrous sodium sulfate (analysis is pure)；
PSA adsorbent (N- propyl ethylenediamine, primery secondary amine) (40-63 μm)；
C18 adsorbent (40-63 μm).
The detection of imidaclothiz in 1 pork of embodiment
The present embodiment sample to be tested: Marketing pork.
Utilize imidaclothiz content in liquid chromatography tandem mass spectrometry detection livestock meat, the method is as follows:
1) sample pre-treatments
After sample to be tested is homogenized with homogenizer, 2.00g sample (being accurate to 0.01g) is accurately weighed in 50mL centrifuge tube
In, 10mL acetonitrile, 0.1mL formic acid, 1.00g sodium chloride, 4.00g anhydrous sodium sulfate is added.Tighten vortex oscillation after centrifuge tube lid
1min is extracted, at 10 DEG C, is centrifuged 5min in 5000r/min.
Upper organic phase is shifted, the 25mL centrifuge tube equipped with 50mg PSA adsorbent and 150mg C18 adsorbent is transferred to
In.Vortex oscillation 1min is centrifuged 5min in 5000r/min at 10 DEG C after tightening centrifuge tube lid.
Supernatant is shifted, nitrogen is blown to dry.It is redissolved with the acetonitrile solution of 1.00mL 50%, through 0.22 μm of miillpore filter mistake
After filter, as test sample liquid for liquid chromatography tandem mass spectroscopy.
2) liquid phase chromatogram condition
C18 chromatographic column, mobile phase are acetonitrile (A) and 0.1% formic acid/aqueous solution (B), and gradient elution program is as follows:
| Time/minute | Mobile phase A/% | Mobile phase B/% |
| 0-1.0 | 5 | 95 |
| 1.0-4.0 | 5-95 | 95-5 |
| 4.0-5.0 | 95 | 5 |
| 5.0-5.1 | 95-5 | 5-95 |
| 5.1-8.0 | 5 | 95 |
35 DEG C of column temperature, flow velocity 0.30mL/min, 10 μ L of sample volume.
3) Mass Spectrometry Conditions
Mass spectrum uses electric spray ion source cation scan pattern (ESI+), and detection mode is more reaction detection modes
(MRM), ion source temperature is 550 DEG C, and electron spray voltage is 5500V, atomization gas pressure 0.050MPa, auxiliary heating atmospheric pressure
0.050MPa, gas curtain atmospheric pressure 0.015MPa.
4) calibration curve
Take 5 parts, every part of 2.00g of negative pork matrix, then by the imidaclothiz standard working solution of 50ng/mL respectively with 20 μ L,
40 μ L, 100 μ L, 200 μ L, the volume of 400 μ L are added in negative pork matrix components, at the method for pre-treatment
This 5 parts of solution, are finally implanted sequentially in liquid chromatograph-mass spectrometer by reason, and measuring corresponding peak area is respectively 5102,
18035,49427,112256,221843, it is 1.0ng/mL, 2.0ng/ that corresponding concentration, which is calculated, in the additive amount according to imidaclothiz
The standard series of mL, 5.0ng/mL, 10ng/mL, 20ng/mL, peak area is corresponding with concentration, it is calculated using least square method,
Obtaining imidaclothiz matrix addition calibration curve is Y=11431X-5540.8R2=0.9994.Wherein, Y indicates response, and X is indicated
Concentration.
Imidaclothiz characteristic ion mass chromatogram is shown in Fig. 1, mass chromatography Fig. 2 of imidaclothiz in pork matrix.
5) result calculates
Sample to be tested in gained test sample liquid injection liquid chromatograph-mass spectrometer, is measured corresponding after pre-treatment
Peak area be 107862, by standard curve obtain imidaclothiz in sample solution concentration be 9.92ng/mL.
The content of imidaclothiz is calculated by formula (1) in sample:
X=C × V/m ... ... ... ... ... (1)
In formula (1):
X --- the content of imidaclothiz in sample to be tested, unit are ng/kg or micro- gram per liter (μ g/kg)；
C --- the concentration of imidaclothiz in resulting test sample liquid, 9.92ng/mL are calculated by standard curve；
V --- the final constant volume of test sample liquid, 1.00mL；
M --- sample to be tested weight, 2.00g；
It is finally calculated by calculation formula, the residual content of imidaclothiz is 4.96 μ g/kg in sample.
The detection of imidaclothiz in 2 beef of embodiment
The present embodiment sample to be tested: commercially available beef.
Detection method is same as Example 1.
The feminine gender beef matrix sample according to obtained by the present embodiment, measuring corresponding peak area is respectively 4977,17526,
46355,103982,213536, according to imidaclothiz additive amount be calculated corresponding concentration be 1.0ng/mL, 2.0ng/mL,
The standard series of 5.0ng/mL, 10ng/mL, 20ng/mL, peak area is corresponding with concentration, it is calculated, is obtained using least square method
It is Y=10970X-6094.4R that imidaclothiz matrix, which adds calibration curve,2=0.9997.Wherein, Y indicates response, and X indicates dense
Degree.
The mass chromatogram of imidaclothiz is shown in Fig. 3 in beef matrix.
Sample to be tested in gained test sample liquid injection liquid chromatograph-mass spectrometer, is measured corresponding after pre-treatment
Peak area be 102150, by standard curve obtain imidaclothiz in sample solution concentration be 9.87ng/mL.
It is finally calculated by calculation formula, the residual content of imidaclothiz is 4.94 μ g/kg in sample.
The detection of imidaclothiz in 3 mutton of embodiment
The present embodiment sample to be tested: commercially available mutton.
Detection method is same as Example 1.
The feminine gender mutton matrix sample according to obtained by the present embodiment, measuring corresponding peak area is respectively 5298,19687,
56540,124921,248625, according to imidaclothiz additive amount be calculated corresponding concentration be 1.0ng/mL, 2.0ng/mL,
The standard series of 5.0ng/mL, 10ng/mL, 20ng/mL, peak area is corresponding with concentration, it is calculated, is obtained using least square method
It is Y=12813X-6366.1R that imidaclothiz matrix, which adds calibration curve,2=0.9996.Wherein, Y indicates response, and X indicates dense
Degree.
The mass chromatogram of imidaclothiz is shown in Fig. 4 in mutton matrix.
As a result it calculates
By sample to be tested after pre-treatment, obtained the sample solution to be tested is injected in liquid chromatograph-mass spectrometer, is measured corresponding
Peak area be 240558, by standard curve obtain imidaclothiz in sample solution concentration be 19.27ng/mL.
It is finally calculated by calculation formula, the residual content of imidaclothiz is 9.64 μ g/kg in sample.
The detection of imidaclothiz in 4 chicken of embodiment
The present embodiment sample to be tested: commercially available chicken.
Detection method is same as Example 1.
The feminine gender chicken matrix sample according to obtained by the present embodiment, measuring corresponding peak area is respectively 5187,18604,
55231,110503,237761, according to imidaclothiz additive amount be calculated corresponding concentration be 1.0ng/mL, 2.0ng/mL,
The standard series of 5.0ng/mL, 10ng/mL, 20ng/mL, peak area is corresponding with concentration, it is calculated, is obtained using least square method
It is Y=12154X-6909.5R that imidaclothiz matrix, which adds calibration curve,2=0.9994.Wherein, Y indicates response, and X indicates dense
Degree.
The mass chromatogram of imidaclothiz is shown in Fig. 5 in mutton matrix.
As a result it calculates
By sample to be tested after pre-treatment, obtained the sample solution to be tested is injected in liquid chromatograph-mass spectrometer, is measured corresponding
Peak area be 225102, by standard curve obtain imidaclothiz in sample solution concentration be 19.27ng/mL.
It is finally calculated by calculation formula, the residual content of imidaclothiz is 9.55 μ g/kg in sample.
The detection (solid phase extraction) of imidaclothiz in 1 pork of comparative example
Take with the identical pork sample of embodiment 1, after being homogenized with homogenizer, accurately weigh 2.00g sample and (be accurate to
0.01g) in 50mL centrifuge tube, 10mL acetonitrile, 0.1mL formic acid, 1.00g sodium chloride, 4.00g anhydrous sodium sulfate is added.It tightens
Vortex oscillation extracts 1min after centrifuge tube lid, at 10 DEG C, is centrifuged 5min in 5000r/min.
Upper organic phase is shifted, is transferred on C18 solid-phase extraction column, 3.00mL water is successively used, the elution of 3.00mL methanol is solid
Phase extraction column discards leacheate, is then eluted with 5% ammoniated methanol of 5.00mL, collects eluent into 10mL centrifuge tube, nitrogen
It is blown to dry.It is redissolved with the acetonitrile solution of 1.00mL 50%, for Liquid Chromatography-Tandem Mass Spectrometry after 0.22 μm of filtering with microporous membrane
Measurement.
Liquid phase chromatogram condition and Mass Spectrometry Conditions are same as Example 1.
The mass chromatogram of this comparative example imidaclothiz is shown in Fig. 6.
As a result, it has been found that parent ion 261.9 and daughter ion 181.1 (quota ion) and daughter ion 122.1 (qualitative ion),
Non- appearance at 3.96min determines that imidaclothiz is not detected in the sample to be tested.
This comparative example, which is used, not to be detected but with the identical sample of embodiment 1 using solid phase extraction progress pre-treatment
It is remained to imidaclothiz, illustrates that the method for solid phase extraction is not able to satisfy the demand for detecting imidaclothiz in livestock meat sample.
The detection (gas chromatography mass spectrometry method) of imidaclothiz in 2 pork of comparative example
Pretreatment
Take with the identical pork sample of embodiment 1, after being homogenized with homogenizer, weigh 10g sample in 50mL plastics from
In heart pipe, the wetting of 2mL water is added, adds 40mL acetonitrile ultrasonic extraction 10min, is centrifuged 10min, supernatant with 4 000r/min
Pour into round-bottomed flask.It repeats to extract 1 time, combined extract after concentration, washs round-bottomed flask, mistake with 5% methanol aqueous solution of 5mL
For gas phase chromatographic tandem mass spectroscopy after 0.25 μm of mixed cellulose ester membrane.
GC conditions
Chromatographic column: J&W DB-1701MS quartz capillary chromatographic column (30m × 0.25mm × 0.25 μm)；Temperature program: just
90 DEG C of beginning temperature, rise to 170 DEG C with 30 DEG C/min, keep 1min, rise to 255 DEG C with 8 DEG C/min, keep 1min, with 30 DEG C/
Min rises to 280 DEG C, keeps 10min；Carrier gas (He) flow velocity 1.0mL/min, 280 DEG C of injector temperature；1 μ L of sample volume；Split ratio
5∶1。
Mass Spectrometry Conditions
Electron bombardment (EI) ion source: electron energy 70eV；280 DEG C of transmission line temperature；230 DEG C of ion source temperature；Quadrupole
150 DEG C of bar temperature；Solvent delay 3.5min；It selects ion scan mode (SIM).
The mass chromatogram of this comparative example imidaclothiz is shown in Fig. 7.
As a result, it has been found that monitored ion 126,152,221, non-appearance, determines in the sample to be tested at 23.68min
Imidaclothiz is not detected.
This comparative example is used, and it is residual to be not detected imidaclothiz using gas chromatography mass spectrometry method with the identical sample of embodiment 1
It stays, illustrates that gas chromatography mass spectrometry method is not able to satisfy the demand for detecting imidaclothiz in livestock meat sample.
Experimental example 1
Since imidaclothiz has a N- nitroguanidine structure, therefore it is with thermal instability.Traditional QuEChERS method, is being extracted
When in order to more fully be distributed in organic phase after being saturated target compound in water phase, anhydrous magnesium sulfate can be added.And nothing
Water magnesium sulfate with after the contact with moisture in sample can it is highly exothermic, cause imidaclothiz at the extraction heat decompose generate loss.
Pre-treatment step is optimized in the present invention, has studied the inorganic salts extractant that different proportion is added to targeted
The influence for closing object extraction effect, has finally determined a kind of pre-treatment scheme of optimization.
Sample to be tested is Marketing pork (same as Example 1), and sample-pretreating method and specific detection method (contain liquid phase
Chromatographic condition and Mass Spectrometry Conditions) it is substantially the same manner as Example 1, difference is only that inorganic salts used are different.
After sample is weighed 8 parts in parallel, imidaclothiz standard substance is added in every part of sample, makes 20.0 μ g/ of its additive amount
Kg, then being separately added into the inorganic salts of acetonitrile and different proportion and formic acid adjustment pH value is added is 2.70, it is fixed after extracting, purifying
Hold, calculates the rate of recovery after upper machine measurement.It the results are shown in Table 1.
Influence (n=8) of the inorganic salts extractant of 1 different proportion of table to target compound extraction recovery
As shown in Table 1, such as the 1st group, inorganic salts are added without, then imidaclothiz is mainly dissolved in brought moisture in sample
In, it is not extracted completely by acetonitrile, the rate of recovery only has 44.81%.Sodium chloride is only added at the 2nd group, extraction, then diuril
Quinoline still cannot be adequately assigned to organic phase at the extraction, and the rate of recovery only has 69.75%.It is only added in the 3rd group and the 4th group
When anhydrous magnesium sulfate or anhydrous sodium sulfate, the rate of recovery improves 4.62% and 11.07% compared to the 2nd group, but still relatively low.?
5th group, while when sodium chloride and anhydrous magnesium sulfate is added, the rate of recovery improves 15.71% compared to the 2nd group, but due to anhydrous
The exothermic effects of magnesium sulfate, the imidaclothiz for resulting in a part produce loss.At the 6th group to the 9th group, it is anhydrous to test reduction
The content of magnesium sulfate and the content for improving anhydrous sodium sulfate, rate of recovery is increase gradually to 92.08% during this.Extremely at the 10th group
It 15th group, has studied under the same conditions, increases influence of the sodium chloride content to the rate of recovery, the results showed that, anhydrous sulphur is being added
After sour magnesium or anhydrous sodium sulfate, the simple content for increasing sodium chloride has no longer improved the rate of recovery of imidaclothiz.So in conjunction with upper
State experimental result and for save reagent the considerations of, the present invention finally determined inorganic salts extractant be 1.00g sodium chloride and
The assembled scheme of 4.00g anhydrous sodium sulfate.
Experimental example 2
Imidaclothiz is stable in acid condition, and easily decomposes under alkaline condition, so control pH value is to protect at the extraction
Demonstrate,prove the good key of the rate of recovery.The present invention has studied the rate of recovery of the formic acid of addition various concentration respectively, to determine formic acid most
Good addition concentration.
Sample to be tested is Marketing pork (same as Example 1), and sample-pretreating method and specific detection method (contain liquid phase
Chromatographic condition and Mass Spectrometry Conditions) it is substantially the same manner as Example 1, difference is only that the pH value of Extraction solvent is different.
After sample is weighed 8 parts in parallel, imidaclothiz standard substance is added in every part of sample, makes 20.0 μ g/ of its additive amount
Kg, then it is separately added into the formic acid adjustment pH value of acetonitrile and different volumes, 1.00g sodium chloride and 4.00g anhydrous slufuric acid is then added
Sodium extracts, constant volume after purification, calculates the rate of recovery after upper machine measurement.It the results are shown in Table 2.
Influence (n=8) of the formic acid content of 2 different proportion of table to target compound extraction recovery
As shown in Table 2, in the 1st group of test, since-NO2 the structure on imidaclothiz molecule is strong electron-withdrawing group group, so that
C atom on C=N group adjacent thereto has the trend of strong adsorption charge, when formic acid tune is not added in Extraction solvent
When whole pH value, which leads to imidaclothiz molecule point so that nucleophilic substitution occur
Solution, so the rate of recovery of imidaclothiz only has 66.75%.At the 2nd group to the 6th group, with the increase of formic acid content, pH value gradually under
It drops, the resolution ratio of imidaclothiz gradually decreases in extraction process, and the rate of recovery is also gradually promoted.It is (molten when formic acid is added to 0.10ml
Liquid pH value is the 2.70) rate of recovery 93.67%.Then, at the 7th group to the 8th group, the additive amount of formic acid, the rate of recovery are continued growing
Also it no longer improves.Therefore the present invention selects the formic acid (solution ph 2.70) that 0.10mL is added in Extraction solvent.
The optimization of 3 chromatographic condition of experimental example
The prior art mostly uses isocratic elution for the analysis measurement of imidaclothiz raw medicine ingredient, and in C18 chromatographic column,
Imidaclothiz belongs to the compound retained more by force.Since protein in livestock meat and fat content are high, and because of fatty acids, ammonia
The impurity such as base acid, inositol, carnosine, nucleotide, are easy to interfere the analysis of target compound.
For this purpose, the present invention has attempted a variety of liquid phase chromatogram conditions, it is specific as follows.
Chromatographic condition 1
Chromatographic column: Thermo Hypersil GOLD C18 chromatographic column, 1.9 μm of partial size, 150mm × 2.1mm；Column temperature: 40
℃；Flow velocity 0.20mL/min, sample volume: 10 μ L；0.1% formic acid water of mobile phase A, Mobile phase B acetonitrile；Condition of gradient elution is shown in
Table 3.
The mobile phase and condition of gradient elution of 3 chromatographic condition 1 of table
| Time/minute | Mobile phase A/% | Mobile phase B/% |
| 0-4.00 | 90-50 | 10-50 |
| 4.00-15.00 | 50-40 | 50-60 |
| 15.00-23.00 | 40-20 | 60-80 |
| 23.00-30.00 | 20-5 | 80-95 |
| 30.00-35.00 | 5 | 95 |
| 35.00-35.01 | 5-90 | 95-10 |
| 35.01-50.00 | 90 | 10 |
Chromatographic condition 2
Chromatographic column: Waters BEH-C18 chromatographic column, 1.7 μm of partial size, 50mm × 2.1mm；35 DEG C of column temperature；Flow velocity
0.30mL/min；10 μ L of sample volume；Mobile phase A acetonitrile, 0.1% aqueous formic acid of Mobile phase B；Condition of gradient elution is shown in Table 4.
The mobile phase and condition of gradient elution of 4 chromatographic condition 2 of table
| Time/minute | Mobile phase A/% | Mobile phase B/% |
| 0-1.00 | 5 | 95 |
| 1.00-4.00 | 5-95 | 95-5 |
| 4.00-5.00 | 95 | 5 |
| 5.00-5.10 | 95-5 | 5-95 |
| 5.1-8.0 | 5 | 95 |
Both the above chromatographic condition is tested with the imidaclothiz standard solution of same concentrations, it is sharp, symmetrical to have obtained peak type
Property lechery spectral peak, but the appearance time of chromatographic condition 1 is 6.37min, and the appearance time of chromatographic condition 2 is 3.97min, and color
The total run time of spectral condition 1 has reached 50.00min, and the total run time of chromatographic condition 2 only has 8.00min, from quick inspection
The demand of survey and the angle of reagent needed for saving mobile phase are investigated, and chromatographic condition 2 is with greater advantage.1 institute of chromatographic condition
Corresponding spectrogram is as shown in figure 8, spectrogram corresponding to chromatographic condition 2 is as shown in Figure 9.
So the present invention selects to use mobile phase: A phase, acetonitrile on the basis of numerous studies；B phase, 0.1% formic acid water
Solution；And separating effect is further increased using the method for gradient elution, the impurity interference in matrix is reduced, and can reduce to the greatest extent
Matrix effect when mass ions.
Specific condition of gradient elution is as follows:
| Time/minute | Mobile phase A/% | Mobile phase B/% |
| 0-1.0 | 5 | 95 |
| 1.0-4.0 | 5-95 | 95-5 |
| 4.0-5.0 | 95 | 5 |
| 5.0-5.1 | 95-5 | 5-95 |
| 5.1-8.0 | 5 | 95 |
Other chromatographic conditions: use C18 chromatographic column, 35 DEG C of column temperature, flow velocity 0.30mL/min, 10 μ L of sample volume.
The optimization of 4 Mass Spectrometry Conditions of experimental example
Under electric spray ion source mode, cation scan pattern (ESI+) and anion scan pattern have been attempted respectively
(ESI-), the signal obtained due to cation scan pattern (ESI+) is stronger, thus it is final determine with electric spray ion source just from
Sub- scan pattern (ESI+) is detected.And based on this, it attempts to test signal under the electron spray voltage of 1000-6500V
Intensity finally obtains electron spray voltage in 5500V, the strongest result of signal.And atomization gas pressure is tested respectively, assists adding
The influence of hot gas pressure and gas curtain atmospheric pressure to signal strength.Obtained optimized parameter is atomization gas pressure 0.050MPa, auxiliary
Heat atmospheric pressure 0.050MPa, gas curtain atmospheric pressure 0.015MPa.That has then attempted different energy levels removes cluster voltage and corresponding
Parent ion karyoplasmic ratio, it is final determine 38.2V remove cluster voltage under using the ion that karyoplasmic ratio is 261.9 as parent ion.Then
Daughter ion scanning is carried out, the quota ion that karyoplasmic ratio is 181.1 is obtained when collision voltage is 22.84V, is in collision voltage
The qualitative ion that karyoplasmic ratio is 122.1 is obtained when 40.27V.
For the accuracy for improving testing result, the mass spectrometry parameters that the present invention optimizes are as follows:
Mass spectrum uses electric spray ion source cation scan pattern (ESI+), and detection mode is more reaction detection modes
(MRM), ion source temperature is 550 DEG C, and electron spray voltage is 5500V, atomization gas pressure 0.050MPa, auxiliary heating atmospheric pressure
0.050MPa, gas curtain atmospheric pressure 0.015MPa.
5 methodology validation of experimental example
By pork, beef, mutton, chicken, pork liver, pig kidney, sheep liver, sheep kidney this 8 class different substrates sample, every class sample
5 parts of samples are weighed respectively, and the sample weighting amount of every part of sample is 2.00g.Be separately added into 5 parts of samples of every class sample 40 μ L,
100 μ L, 200 μ L, 400 μ L, imidaclothiz standard that 1000 μ L concentration are 10ng/mL are molten, and converting its additive amount in the sample is
0.2μg/kg,0.5μg/kg,1.0μg/kg,2.0μg/kg,5.0μg/kg.Sample pre-treatments and liquid are carried out by 1 method of embodiment
The measurement of matter combined instrument.Every part of sample does 8 parallel laboratory tests.It is attached according to GB/T 27404-2007 Good Laboratory control specification
The technical requirements of detection method confirmation in F are recorded, minimum addition concentration of the rate of recovery at 90%~110% is method detection limit.
It is shown in Table 5, it can be seen that imidaclothiz detection limit is 5.0 μ g/kg, relative standard corresponding to method detection limit in different substrates
Deviation is between 2.4%~3.2%.
The rate of recovery of imidaclothiz and precision measurement result (n=8) in 5 different substrates of table
Although above the present invention is described in detail with a general description of the specific embodiments,
On the basis of the present invention, it can be made some modifications or improvements, this will be apparent to those skilled in the art.Cause
This, these modifications or improvements, fall within the scope of the claimed invention without departing from theon the basis of the spirit of the present invention.
Claims (10)
1. the method for imidaclothiz content, is detected using high performance liquid chromatography Mass Spectrometry in a kind of detection livestock meat,
It is characterized in that, includes the steps that sample to be tested pre-treatment；Be wherein, acetonitrile to extraction reagent used in sample to be tested pre-treatment,
Formic acid, sodium chloride and anhydrous sodium sulfate；The volume ratio of acetonitrile and formic acid is 10:0.1；It is acetonitrile and sodium chloride, anhydrous in terms of ml/g
The envelope-bulk to weight ratio of sodium sulphate is respectively 10:1 and 10:4；To sample to be tested extracting solution using PSA adsorbent and C18 adsorbent into
Row adsorption cleaning, wherein the weight ratio of PSA adsorbent and C18 adsorbent is 1:3.
2. the method according to claim 1, wherein in terms of ml/g, in the extraction reagent acetonitrile with to test sample
The envelope-bulk to weight ratio of product is 10:(1-4), preferably 10:2.
3. the method according to claim 1, wherein the sample to be tested pre-treating method is as follows:
After sample to be tested homogenate, 2.00g sample (being accurate to 0.01g) is accurately weighed in 50mL centrifuge tube, and 10mL is added
Acetonitrile, 0.1mL formic acid, 1.00g sodium chloride, 4.00g anhydrous sodium sulfate；Vortex oscillation extracts 1min, at 10 DEG C, in 5000r/
Min is centrifuged 5min；
Transfer upper organic phase is to being equipped in the 25mL centrifuge tube of 50mg PSA adsorbent and 150mg C18 adsorbent；Whirlpool vibration
1min is swung, is centrifuged 5min at 10 DEG C, in 5000r/min；
Supernatant is shifted, nitrogen is blown to dry；It is redissolved with the acetonitrile solution of 1.00mL 50%, after 0.22 μm of filtering with microporous membrane,
As test sample liquid, for liquid chromatography tandem mass spectroscopy.
4. method according to claim 1-3, which is characterized in that liquid phase chromatogram condition is as follows:
Mobile phase: A phase, acetonitrile；B phase, 0.1% aqueous formic acid；
Gradient elution is carried out using following condition:
5. according to the method described in claim 4, it is characterized in that, liquid chromatogram use C18 chromatographic column and/or 35 DEG C of column temperature,
And/or 10 μ L of flow velocity 0.30mL/min and/or sample volume.
6. method according to claim 1-5, which is characterized in that mass spectrometry parameters are as follows:
7. according to the method described in claim 6, it is characterized in that, mass spectrum uses electric spray ion source cation scan pattern
(ESI+), detection mode is more reaction detection modes (MRM), and ion source temperature is 550 DEG C, and electron spray voltage is 5500V, atomization
Atmospheric pressure 0.050MPa, auxiliary heating atmospheric pressure 0.050MPa, gas curtain atmospheric pressure 0.015MPa.
8. method according to claim 1-7, which is characterized in that carry out quantitative analysis using calibration curve method.
9. the method according to claim 1, wherein including the following steps:
1) sample pre-treatments
After sample to be tested is homogenized with homogenizer, 2.00g sample (being accurate to 0.01g) is accurately weighed in 50mL centrifuge tube, is added
Enter 10mL acetonitrile, 0.1mL formic acid, 1.00g sodium chloride, 4.00g anhydrous sodium sulfate.Vortex oscillation is extracted after tightening centrifuge tube lid
1min is centrifuged 5min in 5000r/min at 10 DEG C.
Upper organic phase is shifted, is transferred in the 25mL centrifuge tube equipped with 50mg PSA adsorbent and 150mg C18 adsorbent.It twists
Vortex oscillation 1min after tight centrifuge tube lid is centrifuged 5min in 5000r/min at 10 DEG C.
Supernatant is shifted, nitrogen is blown to dry.It is redissolved with the acetonitrile solution of 1.00mL 50%, after 0.22 μm of filtering with microporous membrane,
As test sample liquid for liquid chromatography tandem mass spectroscopy；
2) liquid phase chromatogram condition
C18 chromatographic column, mobile phase are acetonitrile (A) and 0.1% formic acid/aqueous solution (B), and gradient elution program is as follows:
35 DEG C of column temperature, flow velocity 0.30mL/min, 10 μ L of sample volume；
3) Mass Spectrometry Conditions
Mass spectrum uses electric spray ion source cation scan pattern (ESI+), and detection mode is more reaction detection modes (MRM), from
Source temperature is 550 DEG C, and electron spray voltage is 5500V, atomization gas pressure 0.050MPa, and auxiliary heats atmospheric pressure 0.050MPa,
Gas curtain atmospheric pressure 0.015MPa.
4) calibration curve is prepared
Take 5 parts, every part of 2.00g of negative pork matrix, then by the imidaclothiz standard working solution of 50ng/mL respectively with 20 μ L, 40 μ L,
100 μ L, 200 μ L, the volume of 400 μ L are added in negative pork matrix components, are processed to according to the method for pre-treatment, most
This 5 parts of solution are implanted sequentially in liquid chromatograph-mass spectrometer at last, and measuring corresponding peak area is respectively 5102,18035,
49427,112256,221843, according to imidaclothiz additive amount be calculated corresponding concentration be 1.0ng/mL, 2.0ng/mL,
The standard series of 5.0ng/mL, 10ng/mL, 20ng/mL, peak area is corresponding with concentration, it is calculated, is obtained using least square method
Imidaclothiz matrix adds calibration curve；
5) result calculates
Sample to be tested in gained test sample liquid injection liquid chromatograph-mass spectrometer, is measured into corresponding peak after pre-treatment
Area obtains the concentration of imidaclothiz in test sample liquid by standard curve, and further (1) is calculated in sample to be tested as the following formula
Imidaclothiz content；
X=C × V/m ... ... ... ... ... (1)
In formula (1):
X --- the content of imidaclothiz in sample to be tested, unit are ng/kg or micro- gram per liter (μ g/kg)；
C --- the concentration of imidaclothiz in resulting test sample liquid is calculated by standard curve, unit is nanograms per milliliter (ng/
mL)；
V --- the final constant volume of test sample liquid, unit milliliter (mL)；
M --- sample to be tested weight, unit of gram (g).
10. -9 described in any item methods according to claim 1, which is characterized in that the livestock and poultry include pig, ox, sheep, horse, white horse with a black mane
Camel, rabbit, dog, chicken, duck, goose, dove, quail.
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| CN110618218A (en) * | 2019-11-01 | 2019-12-27 | 国家地质实验测试中心 | Analysis method for rapidly screening pesticide and metabolite residues in tea |
| CN111077262A (en) * | 2019-12-30 | 2020-04-28 | 中国农业科学院农业质量标准与检测技术研究所 | A method for identifying nutritional quality of milk |
| CN112730380A (en) * | 2020-12-24 | 2021-04-30 | 江南大学 | SERS method for detecting levamisole hydrochloride in livestock meat |
| CN114384181A (en) * | 2022-01-07 | 2022-04-22 | 中国计量科学研究院 | An improved QuEChERS-ultra performance liquid chromatography-tandem mass spectrometry method for the determination of neonicotinoid pesticides in Chinese cabbage |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110618218A (en) * | 2019-11-01 | 2019-12-27 | 国家地质实验测试中心 | Analysis method for rapidly screening pesticide and metabolite residues in tea |
| CN111077262A (en) * | 2019-12-30 | 2020-04-28 | 中国农业科学院农业质量标准与检测技术研究所 | A method for identifying nutritional quality of milk |
| CN111077262B (en) * | 2019-12-30 | 2022-05-13 | 中国农业科学院农业质量标准与检测技术研究所 | A method for identifying nutritional quality of milk |
| CN112730380A (en) * | 2020-12-24 | 2021-04-30 | 江南大学 | SERS method for detecting levamisole hydrochloride in livestock meat |
| CN114384181A (en) * | 2022-01-07 | 2022-04-22 | 中国计量科学研究院 | An improved QuEChERS-ultra performance liquid chromatography-tandem mass spectrometry method for the determination of neonicotinoid pesticides in Chinese cabbage |
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