CN104713977B - SPE-the liquid chromatography-tandem mass of multiple pyrazoles bactericide in grape wine - Google Patents
SPE-the liquid chromatography-tandem mass of multiple pyrazoles bactericide in grape wine Download PDFInfo
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Abstract
The invention discloses the SPE-liquid chromatography-tandem mass of multiple pyrazoles bactericide in a kind of grape wine, the present invention can measure in grape wine penta benzene pyrrole bacterium amine, fluorine azoles bacterium acid amides, pyrazoles naphthalene bacterium amine, pyrrole imidazoles, biphenyl pyrrole bacterium amine, 6 kinds of pyrazoles bactericide of furametpyr in sample simultaneously. In grape wine sample, add ultra-pure water dilution to obtain liquid to be checked, liquid to be checked, through HLB SPE column purification, uses C18Reversed-phase column separates; Target analytes relatively carries out qualitative analysis with retention time and ion pair information under multiple-reaction monitoring pattern, external standard method is quantitative, this method analysis speed is fast, highly sensitive, reappearance and the degree of accuracy good, provide new detection method for evaluating grape wine sample quality.
Description
Technical field
The invention belongs to food inspection field, relate to SPE-Liquid Chromatography-Tandem Mass Spectrometry (LC-MS/MS), toolBody refers to penta benzene pyrrole bacterium amine, fluorine azoles bacterium acid amides, pyrazoles naphthalene bacterium amine, pyrrole imidazoles, biphenyl pyrrole bacterium amine, furametpyr in a kind of grape wineDeng the detection method of 6 kinds of pyrazoles bactericide, be particularly useful for grape wine.
Background technology
The grape of Production of Wine primary raw material is in field management process, for preventing that disease and pest from occurring, and can spray conventionallyA certain amount of agricultural chemicals, some agricultural chemicals is difficult for removing decomposing in Production of Wine sweat, can remain in to some extent PortugalIn grape wine, bring potential harm to drinking person health. On same fruit juice class or same existence of other crops processing grape wineState problem.
Bactericide is the class low-toxin farm chemicals for preventing and treating the plant disease being caused by various pathogenic microorganisms, mainly refers to killEpiphyte pharmaceutical. At present, because it has efficiently, on low toxicity and pyrazole ring, substituting group can multi-facetedly convert etc. excellent pyrazole compoundGesture, has become one of focus of new type bactericide exploitation. These bactericide have the special mode of action, and have multiple biological livingProperty. For example, pyraclostrobin (Pyraclostrobin) is methoxy acrylic mitochondria electron transfer inhibitor, has shownTo many plant epiphytes inhibitory action widely. And furametpyr (furametpyr) and biphenyl pyrrole bacterium amine (bixafen) belong toSuccinate dehydrogenase inhibitors (SDHI), the compound II succinate dehydrogenase of can Antifungi breathing. In the last few years, multiple pyrroleAzoles fungicide is applied to the plant disease control in agricultural production more and more widely, as cereal, and vegetables and fruit etc.
Therefore, in food product, occur that sterilant residue is not unexpected. Although these pyrazoles bactericide are to environment faciesTo close friend, if but improper use in agricultural product can cause its high residue problem in food, threaten health. Therefore,Set up and measure accurately, reliably penta benzene pyrrole bacterium amine, fluorine azoles bacterium acid amides, pyrazoles naphthalene bacterium amine, pyrrole imidazoles, biphenyl pyrrole bacterium in grape wineThe content of 6 kinds of pyrazoles bactericide such as amine, furametpyr is extremely important.
At present, conventional analytical method can be divided into qualitative analysis, quantitative analysis and qualitative and quantitative analysis technology. Quantitative analysisGeneral chromatographic technique and the hydrolysis and condensation of adopting, chromatographic technique has the method such as gas-chromatography and liquid chromatogram, chromatogram matterSpectrum GC-MS has the method such as liquid chromatograph mass spectrography and gas chromatography-mass spectrography; Qualitative and quantitative analysis will have two concurrentlyThe technology of kind is integrated, and testing result will provide structural information and the quantity information of object simultaneously, non-strong according to EU CommitteeSystem is carried out the regulation of bill 2002/657/EC, and method that forbidden drugs confirm to detection must be able to provide structure aspectsInformation, and to reach 4 confirmation points that this bill specifies.
At present, owing to can following without relevant criterion or document both at home and abroad, therefore, be necessary in grape wine especially grape wine6 kinds of pyrazoles sterilizations such as penta benzene pyrrole bacterium amine, fluorine azoles bacterium acid amides, pyrazoles naphthalene bacterium amine, pyrrole imidazoles, biphenyl pyrrole bacterium amine, furametpyrThe detection method of agent is studied, thereby pyrazoles bactericide in grape wine is monitored, and is domestic Wine Enterprises simultaneouslyWhile exporting to the areas such as European Union, the detection that can provide the regulation that meets the optional execution bill 2002/657/EC of EU CommitteeData.
Summary of the invention
The object of the invention is the shortcoming and defect existing in order to overcome prior art, and provide in a kind of grape wineThe liquid chromatography-tandem mass of pyrazoles bactericide. The method is in conjunction with SPE-liquid chromatography-tandem mass spectrometryMethod, can be to penta benzene pyrrole bacterium amine, fluorine azoles bacterium acid amides, pyrazoles naphthalene bacterium amine, pyrrole imidazoles, biphenyl pyrrole bacterium amine, furametpyr in grape wineMeasure in 6 kinds of pyrazoles bactericide, it is accurate, quick, highly sensitive that the method has advantages of simultaneously, for vinous fastSpeed detects provides reliable detection method support.
For achieving the above object, technical scheme of the present invention is to comprise the following steps:
(1) preparation of testing sample: take 4.7-5.3g wine sample, add ultra-pure water in wine sample, mixAfter obtain liquid to be checked;
(2) purification of liquid to be checked: will fix phase extraction column and carry out pretreatment, solid on liquid to be checked prepared by step ()Phasing extraction column, removes impurity through water and methanol/water solution drip washing, then with penta benzene on the fixing phase extraction column of eluting solvent wash-outPyrrole bacterium amine, fluorine azoles bacterium acid amides, pyrazoles naphthalene bacterium amine, pyrrole imidazoles, biphenyl pyrrole bacterium amine, furametpyr obtain eluent, and eluent is denseAfter contracting enrichment, with methanol solvate dilution and obtain testing sample solution after 0.22 μ m filtering with microporous membrane;
(3) detection of testing sample solution: prepare respectively penta benzene pyrrole bacterium amine, fluorine azoles bacterium acid amides, pyrazoles naphthalene bacterium amine, pyrrole miaowThe hybrid standard working solution of azoles, biphenyl pyrrole bacterium amine and furametpyr solution ladder concentration (0.4,1.0,2.0,5.0,10.0ng/mL), by the testing sample solution in step (two) and hybrid standard working solution at liquid chromatography-tandem mass spectrometry instrumentUpper sample introduction respectively, obtains with penta benzene pyrrole bacterium amine, fluorine azoles bacterium acid amides, pyrazoles naphthalene bacterium amine, pyrrole imidazoles, biphenyl pyrrole bacterium amine in standard liquidWith the concentration of furametpyr be abscissa, then with penta benzene pyrrole bacterium amine, fluorine azoles bacterium acid amides, pyrazoles naphthalene bacterium amine, pyrrole miaow in standard liquidThe working curve that the peak area of azoles, biphenyl pyrrole bacterium amine and furametpyr is ordinate, also has to obtain and can determine penta of parent ionThe one-level mass spectrogram of benzene pyrrole bacterium amine, fluorine azoles bacterium acid amides, pyrazoles naphthalene bacterium amine, pyrrole imidazoles, biphenyl pyrrole bacterium amine and furametpyr, determines femaleAfter ion, adopt daughter ion scanning to obtain second order ms figure, then from second order ms figure, choose quota ion and qualitative ion,Then with working curve to quota ion carry out quantitatively calculating obtain penta benzene pyrrole bacterium amine in testing sample solution, fluorine azoles bacterium acid amides,The concentration of pyrazoles naphthalene bacterium amine, pyrrole imidazoles, biphenyl pyrrole bacterium amine, furametpyr.
Further setting is that the fixing phase extraction column in described step (two) is WatersOasisHLBSPE post, and logicalCross methyl alcohol, water carries out activation processing to SPE post.
Further setting is that the drip washing solvent in described step (two) is that the methanol-water that water and volume ratio are 2/3 mixes moltenLiquid, eluting solvent is methyl alcohol.
Further arrange is that in described step (three), the detected parameters of liquid chromatography-tandem mass spectrometry instrument is:
Chromatographic column: AgilentZORBAXEclipsePlusC18Reversed-phase column;
Flow velocity: 0.25mL/min;
Mobile phase: A is 0.1% acetic acid aqueous solution; B is acetonitrile;
Sample size: 5 μ L;
Chromatogram column temperature: 30oC;
Electric spray ion source: anion scanning, voltage is 4500V;
Ion source temperature: 450oC;
Atomization gas pressure: 50psi;
Assisted gas flow velocity: 40psi;
Gas curtain atmospheric pressure: 20psi;
Collision atmospheric pressure: 20psi.
Principle and advantage of the present invention:
Adopt such scheme, first, the present invention is by adding ultra-pure water to dilute grape wine sample,
Secondly, the present invention also carries out purified treatment to diluting by ultra-pure water the liquid to be checked obtaining, and this purified treatment comprises pureThe process of change and enrichment. First step purifying: first liquid to be checked is passed through to solid phase extraction column, pass through successively through water and methanol/water moltenLiquid drip washing, methanol-eluted fractions; Second step enrichment: by concentrated the liquid nitrogen gas to be checked of purifying in the first step near dry, then add methyl alcohol moltenLiquid dissolve, through 0.22 μ m filtering with microporous membrane, the liquid to be checked being purified. Liquid to be checked after this purification can be to detecting instrumentPollute. The SPE post of SPE in the present invention is WatersOasisHLBSPE post, due to 6 kinds of pyrazoles bactericideThere are differences with the polarity size of other impurity, on solid-phase extraction column, absorption produces and retains difference, then drenches by preferredWash condition and elution requirement, reach the object of purification enrichment spices.
Again, the present invention is for penta benzene pyrrole bacterium amine, fluorine azoles bacterium acid amides, pyrazoles naphthalene bacterium amine, pyrrole imidazoles, biphenyl pyrrole in grape wineThe qualitative and quantitative detection analysis of 6 kinds of pyrazoles microbiocidal compositions such as bacterium amine, furametpyr is by liquid chromatography-tandem mass spectrometry instrument(LC-MS/MS) analyze. First configure one group of step-like standard operation solution, then by standard operation liquid and liquid to be checked in liquid phaseDifference sample introduction on chromatogram-tandem mass spectrometer. The chromatographic peak retention time occurring in liquid to be checked is consistent with standard operation solution, allowsDeviation is less than ± and 2.5%, the standard operation that the relative abundance of the corresponding mass spectrometry ion of this chromatographic peak is suitable with concentration is moltenThe relative abundance of liquid is consistent, and relative abundance deviation is no more than regulation, can determine in this liquid to be checked and contain pyrazoles sterilizationAgent.
Below in conjunction with specification drawings and specific embodiments, the present invention is described further.
Brief description of the drawings
Fig. 1 is 6 kinds of pyrazoles bactericide structure charts in the specific embodiment of the invention, A. penta benzene pyrrole bacterium amine in Fig. 1; B.Pyrrole imidazoles; C. pyrazoles naphthalene bacterium amine; D. furametpyr E. fluorine azoles bacterium acid amides; F. biphenyl pyrrole bacterium amine;
Fig. 2 is 6 kinds of pyrazoles bactericide standard liquids (1.0ng/mL) MRM chromatogram in the specific embodiment of the invention; FigureIn 2, (2-1) is penta benzene pyrrole bacterium amine; (2-2) be pyrrole imidazoles; (2-3) be pyrazoles naphthalene bacterium amine; (2-4) furametpyr; (2-5) fluorine azolesBacterium acid amides; (2-6) biphenyl pyrrole bacterium amine;
Fig. 3 is 6 kinds of pyrazoles bactericide scanning second order ms figure in the specific embodiment of the invention; In Fig. 3, (3-1) is pentaBenzene pyrrole bacterium amine; (3-2) be pyrrole imidazoles; (3-3) be pyrazoles naphthalene bacterium amine; (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 pyrroleImidazoles; (4-3) be pyrazoles naphthalene bacterium amine; (4-4) furametpyr; (4-5) fluorine azoles bacterium acid amides; (4-6) biphenyl pyrrole bacterium amine.
Detailed description of the invention
Below by embodiment, the present invention is specifically described, is only used to further illustrate the present invention, noCan be interpreted as limiting the scope of the present invention, the technician in this field can be according to the content of foregoing invention to the present inventionMake some nonessential improvement and adjustment.
Embodiment 1
Comprise the following steps:
(1) preparation of testing sample: take grape wine sample 5.0g, add 3mL ultra-pure water to mix and obtain liquid to be checked;
(2) Solid phase extraction: get HLBSPE post, with first alcohol and water activation SPE post, get whole liquid to be checked extremely successivelySPE post, then use successively 4～6mL water and 4～6mL methanol/water mixed solution (v/v, 2/3) drip washing SPE post, by SPE post vacuumDrain, SPE post carried out to wash-out with the methyl alcohol of 6～8mL, obtain eluent, eluent is concentrated after, diluted with 2mL methyl alcoholAfter miillpore filter, obtain testing sample solution;
(3) configuration of standard liquid: get penta benzene pyrrole bacterium amine, fluorine azoles bacterium acid amides, pyrazoles naphthalene bacterium amine, pyrrole imidazoles, biphenyl pyrrole bacteriumAmine, furametpyr standard items, be mixed with respectively single mark storing solution that mass concentration is 200mg/L with methyl alcohol, measures useTime, dilute above-mentioned standard reserving solution with methyl alcohol, by penta benzene pyrrole bacterium amine, fluorine azoles bacterium acid amides, pyrazoles naphthalene bacterium amine, pyrrole imidazoles, biphenyl pyrroleBacterium amine, furametpyr are mixed with respectively the hybrid standard working solution of 0.4,1.0,2.0,5.0,10.0ng/mL;
(4) detection of testing sample: by the testing sample solution in step (two) (three) and standard operation solution in liquid phaseOn chromatogram-tandem mass spectrometer, difference sample introduction, obtains with penta benzene pyrrole bacterium amine, fluorine azoles bacterium acid amides, pyrazoles naphthalene bacterium amine, pyrrole in standard liquidThe concentration of 6 kinds of pyrazoles bactericide such as imidazoles, biphenyl pyrrole bacterium amine, furametpyr is abscissa, then with penta benzene pyrrole in standard liquid6 kinds of pyrazoles bactericide such as bacterium amine, fluorine azoles bacterium acid amides, pyrazoles naphthalene bacterium amine, pyrrole imidazoles, biphenyl pyrrole bacterium amine, furametpyr peakArea is the working curve of ordinate, and result shows, 6 kinds of pyrazoles bactericide have good within the scope of 0.4-10ng/mLLinear relationship, R2>=0.9998, be LOQ taking 10 times of signal to noise ratios (S/N) as method quantitative limit, add test through sample and determine 6 kindsThe quantitative limit of pyrazoles bactericide is 0.2ng/g. Also have and obtain penta benzene pyrrole bacterium amine, the fluorine azoles bacterium acyl that can determine parent ionThe one-level mass spectrogram of 6 kinds of pyrazoles bactericide such as amine, pyrazoles naphthalene bacterium amine, pyrrole imidazoles, biphenyl pyrrole bacterium amine, furametpyr, determines femaleAfter ion, adopt daughter ion scanning to obtain second order ms figure, then from second order ms figure, choose quota ion and qualitative ion,Then with working curve to quota ion carry out quantitatively calculating obtain penta benzene pyrrole bacterium amine in testing sample solution, fluorine azoles bacterium acid amides,The concentration of 6 kinds of pyrazoles bactericide such as pyrazoles naphthalene bacterium amine, pyrrole imidazoles, biphenyl pyrrole bacterium amine, furametpyr.
Referring to table 1, it is 6 kinds of pyrazoles bactericide LC-MS/MS testing conditions
Each compound L of table 1 C-MS/MS testing conditions
*MS/MS quota ion pair
Referring to table 2, it is linear equation, coefficient correlation, the quantitative limit of 6 kinds of pyrazoles bactericide
6 kinds of pyrazoles bactericide that are the embodiment of the present invention 1 referring to table 3 add the rate of recovery, precision and quantitative limit.
Table 36 kind of pyrazoles bactericide adds the rate of recovery, precision and quantitative limit (n=6)
Claims (1)
1. SPE-liquid chromatography-tandem mass of multiple pyrazoles bactericide in grape wine, its featureBe to comprise the following steps:
(1) preparation of testing sample: take 4.7-5.3g wine sample, in wine sample, add ultra-pure water, after mixingTo liquid to be checked;
(2) purification of liquid to be checked: will fix phase extraction column and carry out pretreatment, and fix phase on liquid to be checked prepared by step ()Extraction column, removes impurity through water and methanol/water solution drip washing, then with penta benzene pyrrole bacterium on the fixing phase extraction column of eluting solvent wash-outAmine, fluorine azoles bacterium acid amides, pyrazoles naphthalene bacterium amine, pyrrole imidazoles, biphenyl pyrrole bacterium amine, furametpyr obtain eluent, by concentrated eluent richAfter collection, with methanol solvate dilution and obtain testing sample solution after 0.22 μ m filtering with microporous membrane, in described step (two)Fixing phase extraction column is WatersOasisHLBSPE post, and by methyl alcohol, water, SPE post is carried out to activation processing, described stepSuddenly the drip washing solvent in (two) is the methanol-water mixed solution that water and volume ratio are 2/3, and eluting solvent is methyl alcohol;
(3) detection of testing sample solution: prepare respectively penta benzene pyrrole bacterium amine, fluorine azoles bacterium acid amides, pyrazoles naphthalene bacterium amine, pyrrole imidazoles, connectionThe hybrid standard working solution of benzene pyrrole bacterium amine and furametpyr solution ladder concentration, the concentration of this hybrid standard working solution is0.4ng/mL, 1.0ng/mL, 2.0ng/mL, 5.0ng/mL and 10.0ng/mL, by the testing sample in step (two)Solution and hybrid standard working solution be difference sample introduction on liquid chromatography-tandem mass spectrometry instrument, obtains with penta benzene pyrrole in standard liquidThe concentration of bacterium amine, fluorine azoles bacterium acid amides, pyrazoles naphthalene bacterium amine, pyrrole imidazoles, biphenyl pyrrole bacterium amine and furametpyr is abscissa, then with standardIn solution, the peak area of penta benzene pyrrole bacterium amine, fluorine azoles bacterium acid amides, pyrazoles naphthalene bacterium amine, pyrrole imidazoles, biphenyl pyrrole bacterium amine and furametpyr isThe working curve of ordinate, also has and obtains penta benzene pyrrole bacterium amine, fluorine azoles bacterium acid amides, pyrazoles naphthalene bacterium amine, the pyrrole that can determine parent ionThe one-level mass spectrogram of imidazoles, biphenyl pyrrole bacterium amine and furametpyr, determines after parent ion, adopts daughter ion scanning to obtain second order msFigure then chooses quota ion and qualitative ion from second order ms figure, then with working curve, quota ion is carried out quantitativelyCalculate and obtain penta benzene pyrrole bacterium amine, fluorine azoles bacterium acid amides, pyrazoles naphthalene bacterium amine, pyrrole imidazoles, biphenyl pyrrole bacterium amine, furan pyrrole in testing sample solutionThe concentration of bacterium amine,
In described step (three), the detected parameters of liquid chromatography-tandem mass spectrometry instrument is:
Chromatographic column: AgilentZORBAXEclipsePlusC18Reversed-phase column;
Flow velocity: 0.25mL/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: anion scanning, voltage is 4500V;
Ion source temperature: 450 DEG C;
Atomization gas pressure: 50psi;
Assisted gas flow velocity: 40psi;
Gas curtain atmospheric pressure: 20psi;
Collision atmospheric pressure: 20psi.
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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 |
| 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 |
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