CN104713977A - Method for detecting a plurality of pyrazoles bactericides in wine by solid phase extraction, liquid chromatogram and tandem mass spectrum - Google Patents
Method for detecting a plurality of pyrazoles bactericides in wine by solid phase extraction, liquid chromatogram and tandem mass spectrum Download PDFInfo
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- CN104713977A CN104713977A CN201510013290.8A CN201510013290A CN104713977A CN 104713977 A CN104713977 A CN 104713977A CN 201510013290 A CN201510013290 A CN 201510013290A CN 104713977 A CN104713977 A CN 104713977A
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- bacterium amine
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Abstract
The invention discloses a method for detecting a plurality of pyrazoles bactericides in wine by solid phase extraction, liquid chromatogram and tandem mass spectrum. The method is capable of simultaneously detecting six pyrazoles bactericides of penflufen, fluxapyroxad, isopyrazam, rabenzazole, bixafen and furametpyr in a wine sample. According to the invention, a liquid to be detected which is obtained by diluting the wine sample through addition of ultrapure water, the liquid to be detected is purified by a HLB solid phase extraction column, a C18 reversed-phase column is used for separating; a target analysis object and ions perform qualitative analysis on information comparison in a multi-reaction monitoring mode by using reservation time; and an internal standard method is used for quantification. The method has the advantages of fast analysis speed, high sensitivity, good reappearance and accuracy, and provides the novel detection method for wine sample quality.
Description
Technical field
The invention belongs to field of food detection, relate to Solid-Phase Extraction-Liquid Chromatography-Tandem Mass Spectrometry (LC-MS/MS), specifically refer to the detection method of 6 kinds of pyrazoles germifuge such as penta benzene pyrrole bacterium amine, fluorine azoles bacterium acid amides, isopyrazam, pyrrole imidazoles, biphenyl pyrrole bacterium amine, furametpyr in a kind of grape wine, be particularly useful for grape wine.
Background technology
The grape of Production of Wine primary raw material is in field management process; for preventing disease and pest from occurring, usually can spray a certain amount of agricultural chemicals, some agricultural chemicals not easily removes decomposition in Production of Wine sweat; can remain in grape wine to some extent, bring potential harm to drinking person health.There are the problems referred to above equally in same juice or other crops processing grape wine.
Germifuge is the class low-toxin farm chemicals for preventing and treating the plant disease caused by various pathogenic microorganism, mainly refers to fungicide.At present, pyrazole compound because of its have efficiently, the advantage such as low toxicity and pyrazoles ring substituents can multi-facetedly convert, become one of focus of new type bactericide exploitation.These germifuge have the special mode of action, and have multiple biologically active.Such as, pyraclostrobin (Pyraclostrobin) transmits inhibitor for methoxy acrylic Mitochondrial electron, shows many plant epiphytes inhibiting effect widely.And furametpyr (furametpyr) and biphenyl pyrrole bacterium amine (bixafen), belong to succinate dehydrogenase inhibitors (SDHI), can Antifungi breathe compound II succinate dehydrogenase.In the last few years, multiple pyrazoles germifuge by the plant disease control be applied to more and more widely in agricultural production, as cereal, vegetables and fruit etc.
Therefore, occur in food product that sterilant residue is not unexpected.Although these pyrazoles germifuge to close friend to environment facies, if improper use in agricultural product, can cause its high residue problem in food, threaten health.Therefore, the content setting up accurately, reliably measure 6 kinds of pyrazoles germifuge such as penta benzene pyrrole bacterium amine, fluorine azoles bacterium acid amides, isopyrazam, pyrrole imidazoles, biphenyl pyrrole bacterium amine, furametpyr in grape wine is extremely important.
At present, conventional analytical approach can be divided into qualitative analysis, quantitative test and qualitative and quantitative analysis technology.Quantitative test generally adopts chromatographic technique and hydrolysis and condensation, and chromatographic technique has the method such as gas chromatography and liquid chromatography, and hydrolysis and condensation has the method such as liquid chromatograph mass spectrography and gas chromatography-mass spectrography; Qualitative and quantitative analysis then will have two kinds of technology concurrently and be integrated, testing result will provide structural information and the quantity information of object simultaneously, according to the regulation of the optional execution bill 2002/657/EC of EU Committee, carry out confirming the information that the method detected must can provide configuration aspects to forbidden drugs, and 4 confirmation points of this bill regulation will be reached.
At present, owing to can follow without relevant criterion or document both at home and abroad, therefore, be necessary to study the detection method of the 6 kinds of pyrazoles germifuge such as penta benzene pyrrole bacterium amine, fluorine azoles bacterium acid amides, isopyrazam, pyrrole imidazoles, biphenyl pyrrole bacterium amine, furametpyr in grape wine especially grape wine, thus pyrazoles germifuge in grape wine is monitored, when exporting to the areas such as European Union for domestic Wine Enterprises, the detection data of the regulation meeting the optional execution bill 2002/657/EC of EU Committee can be provided simultaneously.
Summary of the invention
The object of the invention is the shortcoming and defect existed to overcome prior art, and the liquid chromatography-tandem mass of pyrazoles germifuge in a kind of grape wine is provided.The method is in conjunction with Solid-Phase Extraction-Liquid Chromatography-Tandem Mass Spectrometry, can measure 6 kinds of pyrazoles germifuge such as penta benzene pyrrole bacterium amine, fluorine azoles bacterium acid amides, isopyrazam, pyrrole imidazoles, biphenyl pyrrole bacterium amine, furametpyrs in grape wine simultaneously, the method has accurate, quick, highly sensitive advantage, for quick detection vinous provides reliable detection method support.
For achieving the above object, technical scheme of the present invention comprises the following steps:
(1) preparation of testing sample: take 4.7-5.3g wine sample, add ultrapure water in wine sample, obtains liquid to be checked after mixing;
(2) purification of liquid to be checked: Stationary liquid extraction column is carried out pre-service, Stationary liquid extraction column on the liquid to be checked that step () is prepared, through water and methanol/water solution drip washing removing impurity, eluent is obtained again with penta benzene pyrrole bacterium amine on eluting solvent wash-out Stationary liquid extraction column, fluorine azoles bacterium acid amides, isopyrazam, pyrrole imidazoles, biphenyl pyrrole bacterium amine, furametpyr, after eluent enrichment method, dilute with methanol solvate and obtain testing sample solution after 0.22 μm of filtering with microporous membrane;
(3) detection of testing sample solution: prepare penta benzene pyrrole bacterium amine respectively, fluorine azoles bacterium acid amides, isopyrazam, pyrrole imidazoles, the hybrid standard working solution (0.4 of biphenyl pyrrole bacterium amine and furametpyr solution ladder concentration, 1.0, 2.0, 5.0, 10.0 ng/mL), the difference sample introduction on liquid chromatography-tandem mass spectrometry instrument by the testing sample solution in step (two) and hybrid standard working solution, obtains with penta benzene pyrrole bacterium amine in standard solution, fluorine azoles bacterium acid amides, isopyrazam, pyrrole imidazoles, the concentration of biphenyl pyrrole bacterium amine and furametpyr is horizontal ordinate, then with penta benzene pyrrole bacterium amine in standard solution, fluorine azoles bacterium acid amides, isopyrazam, pyrrole imidazoles, the peak area of biphenyl pyrrole bacterium amine and furametpyr is the working curve of ordinate, also has the penta benzene pyrrole bacterium amine obtaining and can determine parent ion, fluorine azoles bacterium acid amides, isopyrazam, pyrrole imidazoles, the first mass spectrometric figure of biphenyl pyrrole bacterium amine and furametpyr, after determining parent ion, daughter ion scanning is adopted to obtain second order ms figure, then from second order ms figure, choose quota ion and qualitative ion, then carry out quantitatively calculating obtaining penta benzene pyrrole bacterium amine in testing sample solution to quota ion with working curve, fluorine azoles bacterium acid amides, isopyrazam, pyrrole imidazoles, biphenyl pyrrole bacterium amine, the concentration of furametpyr.
Further setting is the Stationary liquid extraction column in described step (two) is Waters Oasis HLB SPE post, and carries out activation process by methyl alcohol, water to SPE post.
Further setting is the drip washing solvent in described step (two) to be water and volume ratio be 2/3 methanol-water mixed solution, eluting solvent is methyl alcohol.
Further setting is that in described step (three), the detected parameters of liquid chromatography-tandem mass spectrometry instrument is:
Chromatographic column: Agilent ZORBAX Eclipse Plus C
18reversed-phase column;
Flow velocity: 0.25 mL/min;
Mobile phase: A is 0.1% acetic acid aqueous solution; B is acetonitrile;
Sample size: 5 μ L;
Chromatogram column temperature: 30 oC;
Electric spray ion source: negative ion scans, and voltage is 4500V;
Ion source temperature: 450 oC;
Atomization gas pressure: 50 psi;
Assisted gas flow velocity: 40 psi;
Gas curtain atmospheric pressure: 20 psi;
Collision atmospheric pressure: 20 psi.
Principle and advantage of the present invention:
Adopt such scheme, first, the present invention dilutes wine samples by adding ultrapure water,
Secondly, the present invention also carries out purified treatment to diluting by ultrapure water the liquid to be checked obtained, and this purified treatment comprises the process of purifying and enrichment.First step purifying: first by liquid to be checked by solid phase extraction column, pass through through water and methanol/water solution drip washing, methanol-eluted fractions successively; Second step enrichment: the liquid nitrogen gas to be checked of purifying in the first step is concentrated near dry, then adds dissolve with methanol solution, through 0.22 μm of filtering with microporous membrane, the liquid to be checked be purified.Liquid to be checked after this purification then can not pollute detecting instrument.In the present invention, the SPE post of Solid-Phase Extraction is Waters Oasis HLB SPE post, because the polarity size of 6 kinds of pyrazoles germifuge and other impurity there are differences, on solid-phase extraction column, absorption produces and retains difference, then by preferred drip washing condition and elution requirement, the object of purification enrichment spices is reached.
Again, the present invention is analyzed by liquid chromatography-tandem mass spectrometry instrument (LC-MS/MS) for the qualitative and quantitative detection analysis of 6 kinds of pyrazoles microbiocidal compositions such as penta benzene pyrrole bacterium amine, fluorine azoles bacterium acid amides, isopyrazam, pyrrole imidazoles, biphenyl pyrrole bacterium amine, furametpyr in grape wine.First configure one group of step-like standard working solution, then the difference sample introduction on liquid chromatography-tandem mass spectrometry instrument by standard working solution and liquid to be checked.The chromatographic peak retention time occurred in liquid to be checked is consistent with standard working solution, permissible variation is less than ± 2.5 %, the relative abundance of the standard working solution that the relative abundance of the mass spectrometry ion corresponding to this chromatographic peak is suitable with concentration is consistent, and relative abundance deviation is no more than regulation, then can determine in this liquid to be checked containing pyrazoles germifuge.
Below in conjunction with specification drawings and specific embodiments, the present invention is described further.
Accompanying drawing explanation
Fig. 1 is 6 kinds of pyrazoles germifuge structural drawing in the specific embodiment of the invention, A. penta benzene pyrrole bacterium amine in Fig. 1; B. pyrrole imidazoles; C. isopyrazam; D. furametpyr E. fluorine azoles bacterium acid amides; F. biphenyl pyrrole bacterium amine;
Fig. 2 is 6 kinds of pyrazoles germifuge standard solution (1.0 ng/mL) MRM chromatograms in the specific embodiment of the invention; In Fig. 2, (2-1) is penta benzene pyrrole bacterium amine; (2-2) be pyrrole imidazoles; (2-3) be isopyrazam; (2-4) furametpyr; (2-5) fluorine azoles bacterium acid amides; (2-6) biphenyl pyrrole bacterium amine;
Fig. 3 is 6 kinds of pyrazoles germifuge scanning second order ms figure in the specific embodiment of the invention; In Fig. 3, (3-1) is penta benzene pyrrole bacterium amine; (3-2) be pyrrole imidazoles; (3-3) be isopyrazam; (3-4) furametpyr; (3-5) fluorine azoles bacterium acid amides; (3-6) biphenyl pyrrole bacterium amine;
Fig. 4 is specific embodiment of the invention Plays working curve, and in Fig. 4, (4-1) is penta benzene pyrrole bacterium amine; (4-2) be pyrrole imidazoles; (4-3) be isopyrazam; (4-4) furametpyr; (4-5) fluorine azoles bacterium acid amides; (4-6) biphenyl pyrrole bacterium amine.
Embodiment
Below by embodiment, the present invention is specifically described; only be used to further illustrate the present invention; can not be interpreted as limiting the scope of the present invention, the technician in this field can make some nonessential improvement and adjustment according to the content of foregoing invention to the present invention.
Embodiment 1
Comprise the following steps:
(1) preparation of testing sample: take wine samples 5.0g, adds 3 mL ultrapure water mixings and obtains liquid to be checked;
(2) Solid phase extraction: get HLB SPE post, successively with first alcohol and water activation SPE post, get whole liquid to be checked to SPE post, use 4 ~ 6mL water and 4 ~ 6mL methanol/water mixed solution (v/v, 2/3) drip washing SPE post more successively, SPE post vacuum is drained, with the methyl alcohol of 6 ~ 8mL, wash-out is carried out to SPE post, obtain eluent, after eluent is concentrated, after crossing miillpore filter with 2 mL methanol dilution, obtain testing sample solution;
(3) configuration of standard solution: get penta benzene pyrrole bacterium amine, fluorine azoles bacterium acid amides, isopyrazam, pyrrole imidazoles, biphenyl pyrrole bacterium amine, furametpyr standard items, the list mark storing solution that mass concentration is 200 mg/L is mixed with respectively with methyl alcohol, when carrying out mensuration use, with the above-mentioned standard reserving solution of methanol dilution, penta benzene pyrrole bacterium amine, fluorine azoles bacterium acid amides, isopyrazam, pyrrole imidazoles, biphenyl pyrrole bacterium amine, furametpyr are mixed with 0.4 respectively, 1.0,2.0, the hybrid standard working solution of 5.0,10.0 ng/mL;
(4) detection of testing sample: the difference sample introduction on liquid chromatography-tandem mass spectrometry instrument by the testing sample solution in step (two) (three) and standard working solution, obtain with penta benzene pyrrole bacterium amine in standard solution, fluorine azoles bacterium acid amides, isopyrazam, pyrrole imidazoles, biphenyl pyrrole bacterium amine, the concentration of 6 kinds of pyrazoles germifuge such as furametpyr is horizontal ordinate, again with penta benzene pyrrole bacterium amine in standard solution, fluorine azoles bacterium acid amides, isopyrazam, pyrrole imidazoles, biphenyl pyrrole bacterium amine, 6 kinds of pyrazoles germifuge such as furametpyr peak area be the working curve of ordinate, result shows, 6 kinds of pyrazoles germifuge have good linear relationship within the scope of 0.4-10 ng/mL, R
2>=0.9998, with 10 times of signal to noise ratio (S/N ratio)s (S/N) for method quantitative limit and LOQ, add test through sample and determine that the quantitative limit of 6 kinds of pyrazoles germifuge is 0.2 ng/g.Also has the first mass spectrometric figure obtaining and can determine 6 kinds of pyrazoles germifuge such as penta benzene pyrrole bacterium amine, fluorine azoles bacterium acid amides, isopyrazam, pyrrole imidazoles, biphenyl pyrrole bacterium amine, furametpyr of parent ion, after determining parent ion, daughter ion scanning is adopted to obtain second order ms figure, then from second order ms figure, choose quota ion and qualitative ion, then carry out quantitatively calculating the concentration obtaining 6 kinds of pyrazoles germifuge such as penta benzene pyrrole bacterium amine, fluorine azoles bacterium acid amides, isopyrazam, pyrrole imidazoles, biphenyl pyrrole bacterium amine, furametpyr in testing sample solution with working curve to quota ion.
See table 1, it is 6 kinds of pyrazoles germifuge LC-MS/MS testing conditions
each compound L of table 1 C-MS/MS testing conditions
*mS/MS quota ion pair
See table 2, it is linear equation, related coefficient, the quantitative limit of 6 kinds of pyrazoles germifuge
See 6 kinds of pyrazoles germifuge TIANZHU XINGNAO Capsul, precision and quantitative limit that table 3 is the embodiment of the present invention 1.
table 26 kinds of pyrazoles germifuge TIANZHU XINGNAO Capsul, precision and quantitative limit (n=6)
Claims (4)
1. Solid-Phase Extraction-liquid chromatography-tandem mass of multiple pyrazoles germifuge in grape wine, is characterized in that comprising the following steps:
The preparation of testing sample: take 4.7-5.3g wine sample, add ultrapure water in wine sample, obtains liquid to be checked after mixing;
The purification of liquid to be checked: Stationary liquid extraction column is carried out pre-service, Stationary liquid extraction column on the liquid to be checked that step () is prepared, through water and methanol/water solution drip washing removing impurity, eluent is obtained again with penta benzene pyrrole bacterium amine on eluting solvent wash-out Stationary liquid extraction column, fluorine azoles bacterium acid amides, isopyrazam, pyrrole imidazoles, biphenyl pyrrole bacterium amine, furametpyr, after eluent enrichment method, dilute with methanol solvate and obtain testing sample solution after 0.22 μm of filtering with microporous membrane;
The detection of testing sample solution: prepare penta benzene pyrrole bacterium amine respectively, fluorine azoles bacterium acid amides, isopyrazam, pyrrole imidazoles, the hybrid standard working solution (0.4 of biphenyl pyrrole bacterium amine and furametpyr solution ladder concentration, 1.0, 2.0, 5.0, 10.0 ng/mL), the difference sample introduction on liquid chromatography-tandem mass spectrometry instrument by the testing sample solution in step (two) and hybrid standard working solution, obtains with penta benzene pyrrole bacterium amine in standard solution, fluorine azoles bacterium acid amides, isopyrazam, pyrrole imidazoles, the concentration of biphenyl pyrrole bacterium amine and furametpyr is horizontal ordinate, then with penta benzene pyrrole bacterium amine in standard solution, fluorine azoles bacterium acid amides, isopyrazam, pyrrole imidazoles, the peak area of biphenyl pyrrole bacterium amine and furametpyr is the working curve of ordinate, also has the penta benzene pyrrole bacterium amine obtaining and can determine parent ion, fluorine azoles bacterium acid amides, isopyrazam, pyrrole imidazoles, the first mass spectrometric figure of biphenyl pyrrole bacterium amine and furametpyr, after determining parent ion, daughter ion scanning is adopted to obtain second order ms figure, then from second order ms figure, choose quota ion and qualitative ion, then carry out quantitatively calculating obtaining penta benzene pyrrole bacterium amine in testing sample solution to quota ion with working curve, fluorine azoles bacterium acid amides, isopyrazam, pyrrole imidazoles, biphenyl pyrrole bacterium amine, the concentration of furametpyr.
2. Solid-Phase Extraction-the liquid chromatography-tandem mass of multiple pyrazoles germifuge in a kind of grape wine according to claim 2, it is characterized in that: the Stationary liquid extraction column in described step (two) is Waters Oasis HLB SPE post, and carries out activation process by methyl alcohol, water to SPE post.
3. Solid-Phase Extraction-the liquid chromatography-tandem mass of multiple pyrazoles germifuge in a kind of grape wine according to claim 2, it is characterized in that: the drip washing solvent in described step (two) to be water and volume ratio be 2/3 methanol-water mixed solution, eluting solvent is methyl alcohol.
4. Solid-Phase Extraction-the liquid chromatography-tandem mass of multiple pyrazoles germifuge in a kind of grape wine according to claim 2, is characterized in that: in described step (three), the detected parameters of liquid chromatography-tandem mass spectrometry instrument is:
Chromatographic column: Agilent ZORBAX Eclipse Plus C
18reversed-phase column;
Flow velocity: 0.25 mL/min;
Mobile phase: A is 0.1% acetic acid aqueous solution; B is acetonitrile;
Sample size: 5 μ L;
Chromatogram column temperature: 30 DEG C;
Electric spray ion source: negative ion scans, and voltage is 4500V;
Ion source temperature: 450 DEG C;
Atomization gas pressure: 50 psi;
Assisted gas flow velocity: 40 psi;
Gas curtain atmospheric pressure: 20 psi;
Collision atmospheric pressure: 20 psi.
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Cited By (11)
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| CN105548447A (en) * | 2016-01-30 | 2016-05-04 | 崔淑华 | GC (Gas Chromatograph)-EI (Electronic Impact Ionization)-MS (Mass Spectrometry) determining method of residual quantity of fluxapyroxad |
| CN105548446A (en) * | 2016-01-30 | 2016-05-04 | 崔淑华 | Quick GC (Gas Chromatograph)-MS (Mass Spectrometry)/MS determining method of residual quantity of fluxapyroxad |
| CN105548440A (en) * | 2016-01-30 | 2016-05-04 | 崔淑华 | GC (Gas Chromatograph)-EI (Electronic Impact Ionization)-MS (Mass Spectrometry) determining method of residual quantity of penflufen |
| CN105717211A (en) * | 2016-01-30 | 2016-06-29 | 崔淑华 | GC-MS/MS measurement method for penflufen residual amount |
| CN106324133A (en) * | 2016-08-16 | 2017-01-11 | 韩超 | Solid phase extraction-gas chromatography-tandem mass spectrum detection method for amide fungicides in wine |
| CN106706805A (en) * | 2016-11-13 | 2017-05-24 | 云南中烟工业有限责任公司 | High-performance liquid phase-tandem mass spectrometry detection method for interception of bactericide in main stream smoke in cigarette filter tip |
| CN106918663A (en) * | 2016-11-13 | 2017-07-04 | 云南中烟工业有限责任公司 | The efficient liquid phase tandem mass spectrum detection method of bactericide interception in cigarette mainstream flue gas |
| CN108152421A (en) * | 2018-01-29 | 2018-06-12 | 韩超 | The detection method of fluopicolide fungicide in grape wine |
| CN109187785A (en) * | 2018-09-13 | 2019-01-11 | 张云 | The quantitative detecting method of pesticide biphenyl pyrrole bacterium amine in a kind of lotus seeds |
| CN111929376A (en) * | 2020-07-23 | 2020-11-13 | 河南科技学院 | Method for detecting methoxyl pyrazine compounds in wine |
| CN113341016A (en) * | 2021-06-08 | 2021-09-03 | 河南广电计量检测有限公司 | Method for detecting residual bactericide in animal food |
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| CN105548447A (en) * | 2016-01-30 | 2016-05-04 | 崔淑华 | GC (Gas Chromatograph)-EI (Electronic Impact Ionization)-MS (Mass Spectrometry) determining method of residual quantity of fluxapyroxad |
| CN105548446A (en) * | 2016-01-30 | 2016-05-04 | 崔淑华 | Quick GC (Gas Chromatograph)-MS (Mass Spectrometry)/MS determining method of residual quantity of fluxapyroxad |
| CN105548440A (en) * | 2016-01-30 | 2016-05-04 | 崔淑华 | GC (Gas Chromatograph)-EI (Electronic Impact Ionization)-MS (Mass Spectrometry) determining method of residual quantity of penflufen |
| CN105717211A (en) * | 2016-01-30 | 2016-06-29 | 崔淑华 | GC-MS/MS measurement method for penflufen residual amount |
| CN106324133A (en) * | 2016-08-16 | 2017-01-11 | 韩超 | Solid phase extraction-gas chromatography-tandem mass spectrum detection method for amide fungicides in wine |
| CN106706805A (en) * | 2016-11-13 | 2017-05-24 | 云南中烟工业有限责任公司 | High-performance liquid phase-tandem mass spectrometry detection method for interception of bactericide in main stream smoke in cigarette filter tip |
| CN106918663A (en) * | 2016-11-13 | 2017-07-04 | 云南中烟工业有限责任公司 | The efficient liquid phase tandem mass spectrum detection method of bactericide interception in cigarette mainstream flue gas |
| CN108152421A (en) * | 2018-01-29 | 2018-06-12 | 韩超 | The detection method of fluopicolide fungicide in grape wine |
| CN109187785A (en) * | 2018-09-13 | 2019-01-11 | 张云 | The quantitative detecting method of pesticide biphenyl pyrrole bacterium amine in a kind of lotus seeds |
| CN111929376A (en) * | 2020-07-23 | 2020-11-13 | 河南科技学院 | Method for detecting methoxyl pyrazine compounds in wine |
| CN113341016A (en) * | 2021-06-08 | 2021-09-03 | 河南广电计量检测有限公司 | Method for detecting residual bactericide in animal food |
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