CN104597189A - Determining method of Pyrifluquinazon residual quantity - Google Patents
Determining method of Pyrifluquinazon residual quantity Download PDFInfo
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- CN104597189A CN104597189A CN201510047238.4A CN201510047238A CN104597189A CN 104597189 A CN104597189 A CN 104597189A CN 201510047238 A CN201510047238 A CN 201510047238A CN 104597189 A CN104597189 A CN 104597189A
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- MIOBBYRMXGNORL-UHFFFAOYSA-N pyrifluquinazon Chemical compound C1C2=CC(C(F)(C(F)(F)F)C(F)(F)F)=CC=C2N(C(=O)C)C(=O)N1NCC1=CC=CN=C1 MIOBBYRMXGNORL-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 238000000034 method Methods 0.000 title claims abstract description 16
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000007788 liquid Substances 0.000 claims abstract description 25
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000000746 purification Methods 0.000 claims abstract description 8
- 239000011159 matrix material Substances 0.000 claims abstract description 5
- 239000000523 sample Substances 0.000 claims description 56
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 22
- 239000012086 standard solution Substances 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 17
- 239000012224 working solution Substances 0.000 claims description 17
- 150000002500 ions Chemical class 0.000 claims description 15
- 238000000451 chemical ionisation Methods 0.000 claims description 13
- 238000000605 extraction Methods 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 12
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 11
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 11
- 238000003556 assay Methods 0.000 claims description 10
- 235000013399 edible fruits Nutrition 0.000 claims description 10
- 239000000284 extract Substances 0.000 claims description 10
- 239000012046 mixed solvent Substances 0.000 claims description 10
- 235000013311 vegetables Nutrition 0.000 claims description 10
- 238000004458 analytical method Methods 0.000 claims description 9
- 239000007789 gas Substances 0.000 claims description 9
- 238000002098 selective ion monitoring Methods 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 6
- 239000012496 blank sample Substances 0.000 claims description 6
- 238000001819 mass spectrum Methods 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 238000002414 normal-phase solid-phase extraction Methods 0.000 claims description 6
- 239000001632 sodium acetate Substances 0.000 claims description 6
- 235000017281 sodium acetate Nutrition 0.000 claims description 6
- 239000011780 sodium chloride Substances 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 239000006228 supernatant Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- NDAUXUAQIAJITI-UHFFFAOYSA-N albuterol Chemical compound CC(C)(C)NCC(O)C1=CC=C(O)C(CO)=C1 NDAUXUAQIAJITI-UHFFFAOYSA-N 0.000 claims description 3
- 230000005540 biological transmission Effects 0.000 claims description 3
- 238000004364 calculation method Methods 0.000 claims description 3
- 239000012159 carrier gas Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000012544 monitoring process Methods 0.000 claims description 3
- 229960002052 salbutamol Drugs 0.000 claims description 3
- 239000012530 fluid Substances 0.000 claims description 2
- 230000010355 oscillation Effects 0.000 claims description 2
- 230000002000 scavenging effect Effects 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims 1
- 238000001514 detection method Methods 0.000 abstract description 18
- 239000000575 pesticide Substances 0.000 abstract description 10
- 238000011084 recovery Methods 0.000 abstract description 10
- 235000013305 food Nutrition 0.000 abstract description 6
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- 239000000758 substrate Substances 0.000 abstract description 4
- 238000010812 external standard method Methods 0.000 abstract description 2
- YTJSFYQNRXLOIC-UHFFFAOYSA-N octadecylsilane Chemical group CCCCCCCCCCCCCCCCCC[SiH3] YTJSFYQNRXLOIC-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 238000004587 chromatography analysis Methods 0.000 abstract 1
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- 244000061456 Solanum tuberosum Species 0.000 description 6
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- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
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- AVRPFRMDMNDIDH-UHFFFAOYSA-N 1h-quinazolin-2-one Chemical compound C1=CC=CC2=NC(O)=NC=C21 AVRPFRMDMNDIDH-UHFFFAOYSA-N 0.000 description 1
- 241001124076 Aphididae Species 0.000 description 1
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- 235000011430 Malus pumila Nutrition 0.000 description 1
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- 206010029350 Neurotoxicity Diseases 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 206010044221 Toxic encephalopathy Diseases 0.000 description 1
- 241000607479 Yersinia pestis Species 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
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- 239000003242 anti bacterial agent Substances 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
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- KVSLPQXJQYNHIK-UHFFFAOYSA-N c1ccc2ncncc2c1.Cc1ccc(cc1)S(O)(=O)=O.Cc1ccc(cc1)S(O)(=O)=O Chemical compound c1ccc2ncncc2c1.Cc1ccc(cc1)S(O)(=O)=O.Cc1ccc(cc1)S(O)(=O)=O KVSLPQXJQYNHIK-UHFFFAOYSA-N 0.000 description 1
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- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
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- DPJRMOMPQZCRJU-UHFFFAOYSA-M thiamine hydrochloride Chemical compound Cl.[Cl-].CC1=C(CCO)SC=[N+]1CC1=CN=C(C)N=C1N DPJRMOMPQZCRJU-UHFFFAOYSA-M 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
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- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
Abstract
The invention relates to a determining method of Pyrifluquinazon residual quantity. The method comprises the following steps: homogeneously extracting residual Pyrifluquinazon in a sample by using acetonitrile or an acetonitrile solution containing 1% acetic acid; after dispersed purification of an extracting liquid by using an ethidene diamine-N-propyl silane (PSA) and octadecyl silane bonded phase (C18) matrix, detecting by gas chromatography-negative chemical ionization-chromatography (GC-NCI-MS); and establishing a corrected standard curve by using a blank substrate solution without to-be-detected pesticides, and quantifying by an external standard method. According to the method provided by the invention, the average recovery rate is 88.7-96.1%, the average relative standard deviation (RSD) is 4.7-6.9% and the detection limit is lower than 0.81 microg/kg. The determining method has the advantages of being simple and convenient to operate, quick, high in sensitivity, good in repeatability and accurate to qualify and quantify and can satisfy the technical requirement on safety detection of corresponding products in countries such as Korea, Japan and European Union, and thus a powerful technical support for guaranteeing the food safety of people in China and healthy development of foreign export trade is provided.
Description
Technical field
The present invention relates to a kind of assay method of Pyrifluquinazon residual quantity, be more particularly the method adopting Gas Chromatography-Negative chemical ionization source-mass spectrum (GC-NCI-MS) qualitative, quantitative to measure Pyrifluquinazon content residual in vegetables and fruit, belong to the determination techniques field of persticide residue.
Background technology
The invention of Japanese agricultural chemicals company of Pyrifluquinazon system, and the new quinazoline ditosylate salt pesticide of the tool biamide structure developed jointly in Japanese combinatorial chemistry company, to be mainly used on control vegetables, fruit tree and tealeaves the sucking insects such as Phytophthira, aleyrodid class, mealybug class, leafhopper class, thrips class.Chemistry 1-acetyl group-3,4-dihydro-3-by name [(3-pyridylmethyl) is amino]-6-[1,2; 2; the fluoro-1-of 2-tetra-(trifluoromethyl) ethyl]-2-(1H)-quinazolinone, CAS accession number is 337458-27-2, and structural formula is:
Pyrifluquinazon is used for 18 kinds of crops such as vegetables, tea tree and fruit tree on October 20th, 2010 in Japan's registration, and insect is planted in control more than 20.The former medicine pyrifluquinazon of new pesticides that in January, 2013, Environmental Protection in America was deployed on suggestion approval Nichino America company registers and sucks insect as aphid for greenhouse ornamental crops prevention and control, thrips, aleyrodid etc.This pharmacy effect mechanism makes insect stop taking food and then dying of hunger, and can prevent plant tissue from suffering more infringement, with the propagation of some important diseases of limit.In view of this medicament has novel mechanism of action, the insect that known insecticides susceptibility is declined can be prevented and treated well, and fool proof to various natural enemy, be therefore very suitable for pest resistance management and the comprehensive regulation, there is good application prospect and very large application market.
Although Pyrifluquinazon is little to neurotoxicity and Genotoxic Effect, to the toxic effect of testis, liver and blood pressure.Therefore, the Korea S as agricultural product main exit markets such as China's veterinary antibiotics has formulated residue limits standard with Japan to it.The maximum maximum permission quantity of Korea S regulation Pyrifluquinazon on apple and pears is 0.05mg/kg; Japan has formulated pyrifluquinazon and metabolin B (1,2,3,4-tetrahydrochysene-3-[(3-picolyl) amine]-6-[1, the fluoro-1-of 2,2,2-tetra-(trifluoromethyl) ethyl] quinazoline-2-one) be scaled pyrifluquinazon's and residue limits standard, the residue limits be defined on apple, pears, potato is respectively 0.5,1,0.2mg/kg, all the other are all carried out " uniform limit " of 0.01mg/L; European Union carries out " uniform limit " of 0.01mg/L to pyrifluquinazon.
Up to now, there is 1 section abroad about the report of Pyrifluquinazon residues detection method in food, this detection method adopts acetonitrile to extract, liquid liquid distributes and after the purification of silica gel solid-phase extraction column, liquid chromatography-UV-detector (HPLC-UVD) detects Pyrifluquinazon residual quantity; Domesticly only retrieve a patent " a kind of assay method of Pyrifluquinazon residual quantity ", this patent establishes the detection method adopting Liquid Chromatography-Tandem Mass Spectrometry (LC-MS/MS) to measure Pyrifluquinazon residual quantity in vegetables and fruit.Because food substrate is more complicated, preferably adopt when residues of pesticides are analyzed and can carry out accurately detection method qualitatively, as gaschromatographic mass spectrometry, gas chromatography tandem mass spectrum or liquid chromatography tandem mass spectrometry.Use LC-MS/MS to measure food Residual Pesticides in Farm Produce and there is quick, easy, sensitivity advantages of higher, but due to its price costly, a lot of testing agency, enterprise or scientific research institutions do not configure this instrument or configuration number of units is less, during due to different compounds employing LC-MS/MS detection, different mobile phases or chromatographic column need be used, such needs constantly change chromatographic column, mobile phase expend the long time and balance system, and this constrains the application of LC-MS/MS to a certain extent.The gaschromatographic mass spectrometry (GC-NCI-MS) in outfit negative chemical ionization source is analyzed food Residual Pesticides in Farm Produce tool and is had great advantage, Negative chemical ionization (NCI source) is called as mass spectrum " soft ionization source ", to the analysis thing containing electronegativity group, there is high selectivity and high sensitivity, because its characteristic is strong, when utilizing it to carry out retention analysis, matrix interference is little, can carry out qualitative and quantitative analysis very accurately to object.Existing various testing agency and enterprise have all purchased gas chromatograph-mass spectrometer (GCMS) (GC-MS), generally also be provided with Negative chemical ionization (NCI), now a lot of class agricultural chemicals is all containing electronegativity group, and organochlorine and pyrethroid pesticide molecule are mostly containing strong electronegative group such as-F ,-Cl ,-Br or-COO-, organophosphorus pesticide molecule is mostly containing the=electronegativity group such as S ,-OR ,-P ,-O-,-Cl or-P=O, and mostly containing-F group in the novel agrochemical developed in recent years, therefore, use GC-NCI-MS conveniently can realize the multi-residue analysis of Multiple Pesticides, compared with GC-NCI-MS, better antijamming capability can be obtained, lower sensitivity and better selectivity, Pyrifluquinazon belongs to electronegativity compound, but have no the report of the GC-NCI-MS detection method of Pyrifluquinazon residual quantity in vegetables and fruit up to now, therefore, the detection method setting up Pyrifluquinazon residual quantity in Gas Chromatography-Negative chemical ionization source-mass spectrum (GC-NCI-MS) qualitative and quantitative analysis vegetables and fruit is significant.
Summary of the invention
The object of this invention is to provide a kind of assay method of Pyrifluquinazon residual quantity.
For realizing above object, the technical solution adopted in the present invention is: a kind of assay method of Pyrifluquinazon residual quantity, comprises the steps:
(1) extract
Take sample in tool plug centrifuge tube, add acetonitrile or extract 1min containing the acetonitrile solution homogeneous of 1% acetic acid, add the one in sodium chloride or sodium acetate and anhydrous magnesium sulfate, centrifugal after vibration.
(2) purify
Pipette sample extracting solution supernatant in centrifuge tube, add Dispersive solid phase extraction agent, vortex oscillation, centrifugal, draw after a certain amount of scavenging solution nitrogen dries up, dissolve constant volume with acetone/normal hexane mixed solvent that volume ratio is 1/1, after crossing film, treat that Gas Chromatography-Negative chemical ionization source-mass spectrum (GC-NCI-MS) detects.
(3) preparation of standard working solution
When same kind matrix blank sample not containing Pyrifluquinazon is processed by above-mentioned steps (1), (2), obtain sample extraction purification residue, add appropriate solvent and mixed standard solution, vortex mixes, and is mixed with the Pyrifluquinazon series hybrid standard working fluid of at least 3 concentration.
(4) Gas Chromatography-Negative chemical ionization source-mass spectroscopy (GC-NCI-MS) measures
The standard working solution of each concentration gradient in step (3) is carried out GC-NCI-MS mensuration, with the chromatographic peak area of standard working solution, regretional analysis is carried out to its respective concentration, obtain standard working curve; Under the same conditions the sample liquid after purification in step (2) is injected GC-NCI-MS to measure, record the chromatographic peak area of Pyrifluquinazon in sample liquid, substitute into typical curve, obtain Pyrifluquinazon content in sample liquid, then representated by liquid, the Mass Calculation of sample obtains Pyrifluquinazon residual quantity in sample per sample.If Pyrifluquinazon residual quantity exceedes the range of linearity upper limit in upper machine solution, with constant volume solvent, upper machine solution concentration need be diluted within the range of linearity.
Step (1) if in sample dehydrated vegetables and fruit, need sample weighting amount be reduced, and add suitable quantity of water and fully infiltrate.
Add sodium chloride when adopting acetonitrile to extract in step (1) to saltout, add sodium acetate when adopting the acetonitrile solution containing 1% acetic acid to extract and saltout; A certain amount of water need be added when the sample of moisture content less is saltoutd.
The agent of step (2) mesostroma dispersive solid-phase extraction is made up of anhydrous magnesium sulfate, C18 and PSA, and in every volume extract, anhydrous magnesium sulfate, C18 and PSA addition are respectively 150mg, 50mg and 25mg.
In step (4), GC conditions is: chromatographic column: HP-5MS capillary chromatographic column, column length 30m, internal diameter 0.25mm, thickness 0.25 μm; Injector temperature 250 DEG C; Carrier gas: He, not shunt mode sample introduction, sample size: 1 μ L; Constant current mode, flow velocity 1.0mL/min; Heating schedule: initial temperature 60 DEG C keeps 2min, rises to 200 DEG C, then rises to 220 DEG C with the speed of 2 DEG C per minute, then rise to 280 DEG C with the speed of 20 DEG C per minute with the speed of 20 DEG C per minute, keeps 10min; Transmission line temperature: 280 DEG C.
In step (4), Mass Spectrometry Conditions is: ion source temperature 150 DEG C; Quadrupole rod temperature 150 DEG C; Ionization pattern: negative chemical ionization, i.e. NCI pattern, energy 70eV; Scan mode: Salbutamol Selected Ion Monitoring (SIM) pattern, the solvent delay time is 10min, and the ion of monitoring is: 444,337,402,309.
When measuring sample liquid and extraction standard working solution in step (4), if sample liquid Pesticides chromatographic peak retention time agricultural chemicals retention time corresponding to standard solution is consistent, and in the sample mass spectrogram after background correction, selected ion all occurs, and abundance of ions than with the abundance of ions of standard solution than consistent, then can judge to exist in sample liquid this agricultural chemicals; If above-mentioned two conditions can not meet simultaneously, then judge not containing this kind of agricultural chemicals.
Beneficial effect of the present invention is:
The present invention utilizes dispersive solid-phase extraction technology, establish sample-pretreating method that is easy, that also can effectively avoid sample mesostroma to disturb fast, this pre-treating method is applied to the qualitative confirmation of Pyrifluquinazon and quantitatively detection in vegetables and fruit in conjunction with GC-NCI-MS, average recovery rate is 88.7% ~ 96.1%, average relative standard's deviation (RSD) be 4.7% ~ 6.9% detection limit lower than 0.81 μ g/kg, there is easy and simple to handle, quick, accurate, highly sensitive and reproducible advantage.The technical requirement of the countries such as Korea S, Japan, European Union to corresponding product safety detection being met, providing strong technical support by for ensureing that our people's food security and export abroad trade develop in a healthy way.
Accompanying drawing explanation
Fig. 1 is the Selective ion mode chromatogram that the 100ng/mL Pyrifluquinazon be added in blank apple matrix marks liquid.
Fig. 2 is not containing the Selective ion mode chromatogram of the apple blank sample of Pyrifluquinazon.
The Pyrifluquinazon standard working curve that Fig. 3 is is substrate preparation with the apple blank sample not containing Pyrifluquinazon.
Embodiment
Now with following embodiment, the present invention is described, but is not limit the scope of the invention.
The instrument used in embodiment and reagent
T18Basic homogenizer (IKA, Germany); 5810R hydro-extractor (Eppendorf, Germany); MS3 basic model vortex mixer (IKA, Germany); 7890N gas chromatography-5975C mass spectrometer (Agilent, USA); Primary secondary amine (PSA) adsorbent (40 ~ 60 μm), octadecylsilane Bonded Phase (C18) cleanser (40 ~ 60 μm) are all purchased from Anjelen Sci. & Tech. Inc of the U.S..
Reagent: acetonitrile, acetone, normal hexane (HPLC level, Merke, Germany); Acetic acid (HPLC level, CNW, Germany); Anhydrous magnesium sulfate, sodium chloride and sodium acetate are pure for analyzing, all purchased from Chemical Reagent Co., Ltd., Sinopharm Group.
Standard substance: 100mg/L, acetontrile, purchased from German Dr.Ehrenstorfer company.
Embodiment 1: the detection of Pyrifluquinazon residual quantity in apple
(1) sample pre-treatments
Taking apple 10.0g through fully mixing in 50mL centrifuge tube, accurately adding 20mL acetonitrile, homogeneous extracts 1min, adds 3g anhydrous magnesium sulfate and 2g sodium chloride, after vortex 1min, and the centrifugal 5min of 7000r/min.After centrifugal, get 6mL acetonitrile extract and be transferred in the centrifuge tube that 900mg anhydrous magnesium sulfate, 300mg C18 and 150mg PSA are housed, the centrifugal 5min of vortex 1min, 5000r/min.Get 4mL supernatant in nitrogen blowpipe, dry up in 40 DEG C of nitrogen, add acetone/normal hexane mixed solvent dissolved residue that volume ratio is 1/1, after vortex mixed film, move in sample injection bottle and treat that GC-NCI-MS measures.
(2) preparation of standard working solution
By 100ng/mL standard solution volume ratio be 1/1 acetone/normal hexane mixed solvent be diluted to 10ng/mL standard intermediate liquid, by 10 μ g/mL standard solution dilution be made into 5,2,1,0.5,0.2,0.1 μ g/mL standard solution.Apple blank sample not containing Pyrifluquinazon is pressed above-mentioned pre-treatment step process, obtain sample extraction purification residue, acetone/normal hexane mixed solvent and the above-mentioned mixed standard solution of 100 μ L that 900 μ L volume ratios are 1/1 is added in this residue, vortex mixes, and is made into 10,20,50,100,200,500 μ g/L extraction standard working solutions.
(3) Gas Chromatography-Negative chemical ionization source-mass spectroscopy (GC-NCI-MS) measures
The standard working solution of variable concentrations gradient is injected GC-NCI-MS respectively, carries out the quantitative test of Pyrifluquinazon content with external standard method, namely with the chromatographic peak area of standard working solution, regretional analysis is carried out to its respective concentration, obtain typical curve; Under the same conditions sample extracting solution is injected GC-NCI-MS to measure, record the chromatographic peak area of Pyrifluquinazon in sample liquid, substitute into typical curve, obtain Pyrifluquinazon content in sample liquid, then representated by liquid, the Mass Calculation of sample obtains Pyrifluquinazon residual quantity in sample per sample.If Pyrifluquinazon residual quantity exceedes the range of linearity upper limit in upper machine solution, with constant volume solvent, upper machine solution concentration need be diluted within the range of linearity.
Wherein chromatographic condition is:
Chromatographic column: HP-5MS capillary chromatographic column, column length 30m, internal diameter 0.25mm, thickness 0.25 μm.
Injector temperature: 250.0 DEG C, sample introduction pattern: Splitless injecting samples, sample size: 1 μ L.
Carrier gas: He, constant current mode, flow velocity 1.0mL/min.
Stove case heating schedule: initial temperature 60 DEG C keeps 2min, rises to 200 DEG C, then rises to 220 DEG C with the speed of 2 DEG C per minute, then rise to 280 DEG C with the speed of 20 DEG C per minute with the speed of 20 DEG C per minute, keeps 10min;
Transmission line temperature: 280 DEG C.
Wherein, mass spectrometry parameters is:
Ionization pattern: negative chemical ionization, i.e. NCI pattern, energy 70eV.
Ion source temperature: 150 DEG C.
Quadrupole rod temperature 150 DEG C.
Scan mode: Salbutamol Selected Ion Monitoring (SIM) pattern, the solvent delay time is 10min.
The ion of SIM monitoring is: 444,337,402,309, and quota ion is 444.
Qualitative Identification: at identical conditions, if sample liquid Pesticides chromatographic peak retention time agricultural chemicals retention time corresponding to standard solution is consistent, and in the sample mass spectrogram after background correction, selected ion all occurs, and abundance of ions than with the abundance of ions of standard solution than consistent, then can judge to exist in sample liquid this agricultural chemicals; If above-mentioned two conditions can not meet simultaneously, then judge not containing this kind of agricultural chemicals.
With the chromatographic peak area of standard working solution, regretional analysis is carried out to its respective concentration, obtain standard working curve as table 1.
The typical curve of Pyrifluquinazon in table 1 apple bare substrate
| Title | Retention time (min) | Regression equation | Related coefficient |
| Pyrifluquinazon | 22.52 | Y＝53.187X-400.19 | 0.9993 |
Recovery of standard addition and repeatability:
The Pyrifluquinazon standard solution of 10,20, a 200 and 1000 μ g/kg4 concentration level is added in the apple not containing Pyrifluquinazon, add after 30min until agricultural chemicals and carry out the determination of residual amount by above-mentioned treatment step, the sample liquid volume ratio to be measured that 1000 μ g/kg add concentration be 1/1 acetone/normal hexane mixed solvent measure with GC-MS again after diluting 10 times.Mensuration concentration and agricultural chemicals theory are added concentration compare, obtain agricultural chemicals TIANZHU XINGNAO Capsul, each Pitch-based sphere replicate determination 6 times, obtain its relative standard deviation, measurement result is in table 2.As can be seen from Table 2, in 4 mark-on levels, the average recovery rate of Pyrifluquinazon is 88.7% ~ 96.1%, and average relative standard's deviation (RSD) is 4.7% ~ 6.9%, illustrates that the recovery of the inventive method is higher, reproducible.
The recovery of table 2Pyrifluquinazon and repeatability (n=6)
Detection limit:
The Pyrifluquinazon extraction standard working solution of variable concentrations is injected GC-NCI-MS, calculate detection limit with the cycles of concentration (cycles of concentration of apple is 2.0 times) of 3 times of signal to noise ratio (S/N ratio)s of least concentration extraction standard solution chromatographic peak and sample handling processes, detecting of Pyrifluquinazon is limited to 0.86 μ g/kg.
Embodiment 2: the detection of Pyrifluquinazon residual quantity in potato
(1) sample pre-treatments
Take potato 10.0g through fully mixing in 50mL centrifuge tube, after adding 8mL water, accurately add the acetonitrile solution of 20mL containing 1% acetic acid, homogeneous extracts 1min, adds 3g anhydrous magnesium sulfate and 2g sodium acetate, after vortex 1min, and the centrifugal 5min of 7000r/min.After centrifugal, get 6mL acetonitrile extract and be transferred in the centrifuge tube that 900mg anhydrous magnesium sulfate, 300mg C18 and 150mg PSA are housed, the centrifugal 5min of vortex 1min, 5000r/min.Get 4mL supernatant in nitrogen blowpipe, dry up in 40 DEG C of nitrogen, add acetone/normal hexane mixed solvent dissolved residue that volume ratio is 1/1, after vortex after mixing, move in sample injection bottle and treat that GC-NCI-MS measures.
(2) preparation of standard working solution
By 100ng/mL standard solution volume ratio be 1/1 acetone/normal hexane mixed solvent be diluted to 10ng/mL standard intermediate liquid, by 10 μ g/mL standard solution dilution be made into 5,2,1,0.5,0.2,0.1 μ g/mL standard solution.Potato blank sample not containing Pyrifluquinazon is pressed above-mentioned pre-treatment step process, obtain sample extraction purification residue, acetone/normal hexane mixed solvent and the above-mentioned mixed standard solution of 100 μ L that 900 μ L volume ratios are 1/1 is added in this residue, vortex mixes, and is made into 10,20,50,100,200,500 μ g/L extraction standard working solutions.
(3) Gas Chromatography-Negative chemical ionization source-mass spectroscopy (GC-NCI-MS) measures
Operation steps, chromatogram are consistent with the mensuration of Pyrifluquinazon in above-mentioned apple sample with Mass Spectrometry Conditions.
Qualitative Identification:
Consistent with the mensuration of Pyrifluquinazon in above-mentioned apple sample.
Linear relationship:
Carry out regretional analysis with the chromatographic peak area of standard working solution to its respective concentration, obtaining standard working curve is Y=78.78X-846.88, and related coefficient is 0.9993.
Recovery of standard addition and repeatability:
The Pyrifluquinazon standard solution of 10,20 and 500 μ g/kg, 3 concentration levels is added in the potato not containing Pyrifluquinazon, add after 30min until agricultural chemicals and carry out the determination of residual amount by above-mentioned treatment step, the sample liquid volume ratio to be measured that 500 μ g/kg add concentration be 1/1 acetone/normal hexane mixed solvent measure with GC-MS again after diluting 5 times.Mensuration concentration and agricultural chemicals theory are added concentration compare, obtain agricultural chemicals TIANZHU XINGNAO Capsul, each Pitch-based sphere replicate determination 6 times, obtain its relative standard deviation, measurement result is in table 3.As can be seen from Table 3, in 3 mark-on levels, the average recovery rate of Pyrifluquinazon is 91.5% ~ 95.3%, and average relative standard's deviation (RSD) is 4.9% ~ 6.3%, illustrates that the recovery of the inventive method is high, reproducible.
The recovery of table 3Pyrifluquinazon and repeatability (n=6)
Detection limit:
The Pyrifluquinazon extraction standard working solution of variable concentrations is injected GC-NCI-MS, calculate detection limit with the cycles of concentration (cycles of concentration of potato is 2.0 times) of 3 times of signal to noise ratio (S/N ratio)s of least concentration extraction standard solution chromatographic peak and sample handling processes, detecting of Pyrifluquinazon is limited to 0.81 μ g/kg.
Above embodiment is only be described the preferred embodiment of the present invention; not scope of the present invention is limited; under not departing from the present invention and designing the prerequisite of spirit; the various modification that the common engineering in this area is made technical scheme of the present invention and improvement, all should fall in protection domain that claims of the present invention determine.
Claims (5)
1. an assay method for Pyrifluquinazon residual quantity, is characterized in that, said method comprising the steps of:
(1) extract
Take vegetables and fruit sample in tool plug centrifuge tube, add acetonitrile or extract 1min containing the acetonitrile solution homogeneous of 1% acetic acid, centrifugal after adding one in sodium chloride or sodium acetate and anhydrous magnesium sulfate vibration;
(2) purify
Pipette sample extracting solution supernatant in centrifuge tube, add Dispersive solid phase extraction agent, vortex oscillation, centrifugal, get after a certain amount of scavenging solution nitrogen dries up, dissolve constant volume with acetone/normal hexane mixed solvent that volume ratio is 1/1, after crossing film, treat that Gas Chromatography-Negative chemical ionization source-mass spectrum (GC-NCI-MS) detects;
(3) preparation of standard working solution
Same kind matrix blank sample not containing Pyrifluquinazon is processed by above-mentioned steps (1), (2), obtain sample extraction purification residue, add appropriate solvent and mixed standard solution, vortex mixes, and is mixed with the Pyrifluquinazon series hybrid standard working fluid of at least 3 concentration;
(4) mensuration and result calculate
The standard working solution of each concentration gradient in step (3) is carried out GC-NCI-MS mensuration, with the chromatographic peak area of standard working solution, regretional analysis is carried out to its respective concentration, obtain extraction standard working curve; Under the same conditions the sample liquid after purification in step (2) is injected GC-NCI-MS to measure, record the chromatographic peak area of Pyrifluquinazon in sample liquid, substitute into extraction standard curve, obtain Pyrifluquinazon content in sample liquid, then representated by liquid, the Mass Calculation of sample obtains Pyrifluquinazon residual quantity in sample per sample.If Pyrifluquinazon residual quantity exceedes the range of linearity upper limit in upper machine solution, with constant volume solvent, upper machine solution concentration need be diluted within the range of linearity.
2. the assay method of a kind of Pyrifluquinazon residual quantity according to claim 1, is characterized in that, step (1) if in vegetables and fruit sample dehydrated sample, need sample weighting amount be reduced, and add suitable quantity of water and fully infiltrate.
3. the assay method of a kind of Pyrifluquinazon residual quantity according to claim 1, it is characterized in that, sodium chloride need be added when adopting acetonitrile to extract in step (1) to saltout, sodium acetate need be added when adopting the acetonitrile solution containing 1% acetic acid to extract and saltout.
4. the assay method of a kind of Pyrifluquinazon residual quantity according to claim 1, is characterized in that, the agent of step (2) mesostroma dispersive solid-phase extraction is by anhydrous magnesium sulfate, C
18with PSA composition, anhydrous magnesium sulfate, C in every volume extract
18150mg, 50mg and 25mg is respectively with PSA addition.
5. the assay method of a kind of Pyrifluquinazon residual quantity according to claim 1, it is characterized in that, in step (4), GC-NCI-MS analysis condition is: chromatographic column: HP-5MS capillary chromatographic column, column length 30m, internal diameter 0.25mm, thickness 0.25 μm; Injector temperature 250.0 DEG C; Carrier gas: He, not shunt mode sample introduction, sample size: 1 μ L; Constant current mode, flow velocity 1.0mL/min; Heating schedule: initial temperature 60 DEG C keeps 2min, rises to 200 DEG C, then rises to 220 DEG C with the speed of 2 DEG C per minute, then rise to 280 DEG C with the speed of 20 DEG C per minute with the speed of 20 DEG C per minute, keeps 10min; Transmission line temperature: 280 DEG C; Ionization pattern: negative chemical ionization, i.e. NCI pattern, energy 70eV; Ion source temperature 150 DEG C; Scan mode: Salbutamol Selected Ion Monitoring (SIM) pattern, the ion of monitoring is: 444,337,402,309.
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| CN105717221A (en) * | 2016-01-30 | 2016-06-29 | 崔淑华 | GC-EI-MS rapid measurement method for penflufen residual amount |
| CN113960236A (en) * | 2021-10-11 | 2022-01-21 | 大连海洋大学 | Method for determining geosmin and dimethyl isoborneol in fish body based on rapid pretreatment technology |
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