CN108152421A - The detection method of fluopicolide fungicide in grape wine - Google Patents
The detection method of fluopicolide fungicide in grape wine Download PDFInfo
- Publication number
- CN108152421A CN108152421A CN201810083490.4A CN201810083490A CN108152421A CN 108152421 A CN108152421 A CN 108152421A CN 201810083490 A CN201810083490 A CN 201810083490A CN 108152421 A CN108152421 A CN 108152421A
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- Prior art keywords
- fluopicolide
- fungicide
- solution
- grape wine
- ion
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
Abstract
The invention discloses a kind of detection method of fluopicolide fungicide in grape wine, the present invention being capable of fluopicolide fungicide in Accurate Determining wine samples.Include the following steps:The preparation of sample to be tested, the purification of liquid to be checked, the configuration of standard solution and the detection of testing sample solution, this method combination Solid Phase Extraction gas-chromatography bears chemical source tandem mass spectrometry, measure can be carried out at the same time to fluopicolide fungicide in grape wine, accurate, quick, high sensitivity that this method has the advantages that, the quick detection for grape wine provide reliable detection method and support.
Description
Technical field
The invention belongs to Food Inspection Quarantine Techniques fields, are related to organophosphorous pesticides-negative chemical source-series connection matter
The detection method of fluopicolide fungicide in spectrometry (GC-NCI-MS/MS), in particular to a kind of grape wine.
Background technology
With the improvement of people ' s living standards with the enhancing of health perception, grape wine this collection trophism, functionality and
Cultural taste is increasingly liked in the special drink of one by people.Zhejiang is more flourishing as China's southeastern coast economy
Province, in recent years grape wine consumption figure rapid development, particularly import grape wine.The Zhejiang port import grape wine volume of trade is always
Occupy whole nation leading position of the same trade.The hot degree of grape wine consumption market has some idea of.
However, whether import or domestic grape wine, grape is as its most important raw materials for production in field management
Cheng Zhong, to prevent disease, it will usually spray a certain amount of pesticide, some pesticides are not easy in Production of Wine fermentation process
Removal is decomposed, and can be remained in grape wine to some extent, is potentially threatened to drinking person health care belt.2013, U.S.'s ring
In " most dirty fruits and vegetables " blacklist of border working group (EWG) publication, grape ranks third, detects 15 kinds of residue of pesticide ingredients altogether,
And containing pesticide variety in terms of, grape then ranks first, in total containing 64 kinds of different chemical substances.Therefore, grape wine
In Pesticide Residue should not be underestimated.
At present, strict regulations, such as European Standard have done to maximum residue limit of the fluopicolide in food in some countries
Rule regulation：Maximum residue limit is down to 2.0 mg/kg in grape.These regulations while consumer health's interests are protected,
It is important TBT (Technical Barriers to Trade) measure.
Therefore, the content for establishing fluopicolide fungicide in accurately and reliably measure grape wine is extremely important.
At present, conventional analysis method can be divided into qualitative analysis, quantitative analysis and qualitative and quantitative analysis technology.Quantitative analysis
Generally using chromatographic technique and hydrolysis and condensation, chromatographic technique has the methods of gas-chromatography and liquid chromatogram, chromatography matter
Spectrum joint technology has the methods of liquid chromatograph mass spectrography and gas chromatography-mass spectrography；Qualitative and quantitative analysis will then have both two
Kind technology is integrated, and testing result will provide the structural information and quantity information of object simultaneously, non-strong according to EU Committee
System performs the regulation of bill 2002/657/EC, and the method that forbidden drugs are carried out with confirmation detection must be able to provide configuration aspects
Information, and to reach 4 confirmation points as defined in the bill.
At present, due to that can be followed without relevant criterion or document both at home and abroad, therefore, it is necessary to be killed to the fluopicolide in grape wine
The detection method of microbial inoculum is studied, and so as to be monitored to acid amide fungicides in grape wine, while is domestic grape wine enterprise
Industry exports to European Union when area, can provide and meet the optional defined inspection for performing bill 2002/657/EC of EU Committee
Measured data.
Invention content
For overcome the deficiencies in the prior art, the present invention provides a kind of detection sides of fluopicolide fungicide in grape wine
Method.Due to bearing chemical source（NCI）Selectivity it is strong, detection sensitivity significantly improves, fluorine with the enhancing of testing molecule electronegativity
Pyrrole bacterium amine contains chlorobenzene structure, and electronegativity is stronger, therefore selects NCI as the existing preferable selectivity of ion source, and have very high
Sensitivity.Tandem mass spectrum is because using multiple-reaction monitoring（MRM）Pattern can be very good the background interference of removal complex matrices, real
Now to the quantitative analysis of object.Compared with current blanket monopole mass spectrum, have stronger anti-matrix interference ability and
Qualitative, quantitative accuracy.This method combination organophosphorous pesticides-negative chemical source-tandem mass spectrometry, can be in grape wine
Fluopicolide fungicide is carried out at the same time measure, and accurate, quick, high sensitivity that this method has the advantages that, is the quick of grape wine
Detection provides reliable detection method and supports.
To achieve these goals, the present invention provides a kind of detection method of fluopicolide fungicide in grape wine, including
Following steps：
Step 1：The preparation of sample to be tested：0.7-1.3g wine samples are weighed, ultra-pure water, mixing are added in wine sample
After obtain liquid to be checked；
Step 2：The purification of liquid to be checked：Stationary phase extraction column is pre-processed, it will be fixed on a kind of liquid to be checked prepared of step
Phase extraction column removes impurity, then obtain eluent with the fluopicolide on eluting solvent elution stationary phase extraction column through water wash,
After eluent enrichment method, testing sample solution is obtained after 0.22 μm of filtering with microporous membrane；
Step 3：The configuration of standard solution：Compound concentration gradient be respectively 1.0 ng/mL, 2.0 ng/mL, 5.0 ng/mL,
The fluopicolide solution of 10.0 ng/mL, 20.0 ng/mL and 50.0 ng/mL form matrix matching standard working solution；
Step 4：The detection of testing sample solution：By the testing sample solution in step 2 and matrix matching standard working solution
Sample introduction is distinguished on Gas Chromatography-Negative chemical source-tandem mass spectrometer, is obtained with a concentration of horizontal seat of fluopicolide in standard solution
Mark, then using the peak area of fluopicolide in hybrid standard working solution as the working curve of ordinate, also obtaining can determine
The first mass spectrometric figure of the fluopicolide of parent ion after determining parent ion, is scanned using daughter ion and obtains second order ms figure, Ran Houcong
Quota ion and qualitative ion are chosen in second order ms figure, then carries out quantitative calculating to quota ion with working curve, in addition
Standard measure is marked, obtains the concentration of fluopicolide in testing sample solution.
The stationary phase extraction column that the present invention is further arranged in the step 2 is Germany's BESTOWN HR-X SPE columns,
And pass through methanol, water to SPE columns progress activation process.
The eluent that the present invention is further arranged in the step 2 is water, and eluting solvent is ethyl acetate.
The detection parameters that the present invention is further arranged to gas chromatography tandem mass spectrometry instrument in the step four are：
Chromatographic column：HP-5MS, 30m × 0.25mm × 0.25 μm,
Temperature programming：1min is kept at 60 DEG C, then 200 DEG C are warming up to the speed of 30 DEG C of raising per minute, finally with per minute
The speed of 15 DEG C of raising is increased to 300 DEG C and keeps 5min；
Sample size：1μL；
Carrier gas：High-purity helium, purity >=99.999%, flow 1.0mL/min；
Collision gas：High-purity argon gas, purity >=99.999%；
Sample size mouth temperature：240℃；
Ion source：Chemical source negative ion mode（NCI）；Methane makees reaction gas, purity >=99.999%, flow 1.0mL/min；Source
Temperature：200℃.
Interface temperature：250℃；
Using the above scheme, the present invention is diluted wine samples by adding in ultra-pure water, and to being diluted by ultra-pure water
The liquid to be checked arrived carries out purified treatment, which includes the process of purifying and enrichment.The first step purifies：First liquid to be checked is led to
Solid phase extraction column is crossed, is eluted by water wash and ethyl acetate；Second step is enriched with：The liquid nitrogen gas to be checked that will be purified in the first step
Concentration is near dry, then adds in ethyl acetate solution dissolving, through 0.22 μm of filtering with microporous membrane, the liquid to be checked being purified.This is net
Liquid to be checked after change will not then pollute detecting instrument.The SPE columns of Solid Phase Extraction are Germany BESTOWN HR- in the present invention
X SPE columns, absorption, which generates, on solid-phase extraction column retains difference, then by preferably eluting condition and elution requirement, reaches
The purpose of purification enrichment fungicide.
Secondly, the present invention is to pass through gas for the qualitative and quantitative detection analysis of the fluopicolide microbiocidal composition in grape wine
Phase chromatography-negative chemical source-tandem mass spectrum detector (GC-NCI-MS/MS) analysis.It is molten that one group of step-like standard work is first configured
Then standard working solution and liquid to be checked are distinguished sample introduction by liquid on Gas Chromatography-Negative chemical source-tandem mass spectrometer.In liquid to be checked
The chromatographic peak retention time of appearance is consistent with standard working solution, and tolerance is less than ± 2.5 %, the matter corresponding to the chromatographic peak
The relative abundance for composing qualitative ion is consistent with the relative abundance of the comparable standard working solution of concentration, and relative abundance deviation is not
More than regulation, then it can determine in the liquid to be checked and contain acid amide fungicides.
The invention will be further described below in conjunction with the accompanying drawings.
Description of the drawings
Attached drawing 1 is the fluopicolide chemical structural formula in the specific embodiment of the invention；
Attached drawing 2 is fluopicolide fungicide standard solution (1.0 ng/mL) MRM chromatograms in the specific embodiment of the invention；
Attached drawing 3 is that fluopicolide fungicide scans second order ms figure in the specific embodiment of the invention；
Attached drawing 4 is fluopicolide standard working curve in the specific embodiment of the invention.
Specific embodiment
Specific embodiments of the present invention are the detection method of fluopicolide fungicide in grape wine as shown in Figs 1-4, packet
Include following steps：
Step 1：The preparation of sample to be tested：0.7-1.3g wine samples are weighed, ultra-pure water, mixing are added in wine sample
After obtain liquid to be checked；
Step 2：The purification of liquid to be checked：Stationary phase extraction column is pre-processed, it will be fixed on a kind of liquid to be checked prepared of step
Phase extraction column, stationary phase extraction column are Germany's BESTOWN HR-X SPE columns, and impurity is removed, then made with ethyl acetate through water wash
The fluopicolide on stationary phase extraction column is eluted for eluting solvent and obtains eluent, after eluent enrichment method, through 0.22 μm
Testing sample solution is obtained after filtering with microporous membrane；
Step 3：The configuration of standard solution：Compound concentration gradient be respectively 1.0 ng/mL, 2.0 ng/mL, 5.0 ng/mL,
The fluopicolide solution of 10.0 ng/mL, 20.0 ng/mL and 50.0 ng/mL form matrix matching standard working solution；
Step 4：The detection of testing sample solution：By the testing sample solution in step 2 and matrix matching standard working solution
Sample introduction is distinguished on Gas Chromatography-Negative chemical source-tandem mass spectrometer, is obtained with a concentration of horizontal seat of fluopicolide in standard solution
Mark, then using the peak area of fluopicolide in hybrid standard working solution as the working curve of ordinate, also obtaining can determine
The first mass spectrometric figure of the fluopicolide of parent ion after determining parent ion, is scanned using daughter ion and obtains second order ms figure, Ran Houcong
Quota ion and qualitative ion are chosen in second order ms figure, then carries out quantitative calculating to quota ion with working curve, in addition
Standard measure is marked, obtains the concentration of fluopicolide in testing sample solution.The detection parameters of the gas chromatography tandem mass spectrometry instrument
For：
Chromatographic column：HP-5MS, 30m × 0.25mm × 0.25 μm,
Temperature programming：1min is kept at 60 DEG C, then 200 DEG C are warming up to the speed of 30 DEG C of raising per minute, finally with per minute
The speed of 15 DEG C of raising is increased to 300 DEG C and keeps 5min；
Sample size：1μL；
Carrier gas：High-purity helium, purity >=99.999%, flow 1.0mL/min；
Collision gas：High-purity argon gas, purity >=99.999%；
Sample size mouth temperature：240℃；
Ion source：Chemical source negative ion mode（NCI）；Methane makees reaction gas, purity >=99.999%, flow 1.0mL/min；Source
Temperature：200℃.
Interface temperature：250℃.
*MS/MS quota ion pairs
Table 1-fluopicolide fungicide GC-NCI-MS/MS testing conditions
| Compound | Linear equation | Related coefficient | Quantitative limit ng/g |
| Fluopicolide | Y=65.9967X+196.142 | 0.9975 | 1.0 |
The linear equation of table 2-fluopicolide fungicide, related coefficient, quantitative limit
3-4 kinds of acid amide fungicides TIANZHU XINGNAO Capsuls of table, precision (n=6)
The present invention is not limited to above-mentioned specific embodiment, and persons skilled in the art according to the present disclosure, can
To implement of the invention or every design structure using the present invention and thinking using other a variety of specific embodiments, do
Simple change or change, both fall within protection scope of the present invention.
Claims (4)
1. a kind of detection method of fluopicolide fungicide in grape wine, it is characterised in that:Include the following steps：
Step 1：The preparation of sample to be tested：0.7-1.3g wine samples are weighed, ultra-pure water, mixing are added in wine sample
After obtain liquid to be checked；
Step 2：The purification of liquid to be checked：Stationary phase extraction column is pre-processed, it will be fixed on a kind of liquid to be checked prepared of step
Phase extraction column removes impurity, then obtain eluent with the fluopicolide on eluting solvent elution stationary phase extraction column through water wash,
After eluent enrichment method, testing sample solution is obtained after 0.22 μm of filtering with microporous membrane；
Step 3：The configuration of standard solution：Compound concentration gradient be respectively 1.0 ng/mL, 2.0 ng/mL, 5.0 ng/mL,
The fluopicolide solution of 10.0 ng/mL, 20.0 ng/mL and 50.0 ng/mL form matrix matching standard working solution；
Step 4：The detection of testing sample solution：By the testing sample solution in step 2 and matrix matching standard working solution
Sample introduction is distinguished on Gas Chromatography-Negative chemical source-tandem mass spectrometer, is obtained with a concentration of horizontal seat of fluopicolide in standard solution
Mark, then using the peak area of fluopicolide in hybrid standard working solution as the working curve of ordinate, also obtaining can determine
The first mass spectrometric figure of the fluopicolide of parent ion after determining parent ion, is scanned using daughter ion and obtains second order ms figure, Ran Houcong
Quota ion and qualitative ion are chosen in second order ms figure, then carries out quantitative calculating to quota ion with working curve, in addition
Standard measure is marked, obtains the concentration of fluopicolide in testing sample solution.
2. the detection method of fluopicolide fungicide in a kind of grape wine according to claim 1, it is characterised in that：It is described
Stationary phase extraction column in step 2 is Germany's BESTOWN HR-X SPE columns, and pass through methanol, water carries out at activation SPE columns
Reason.
3. the detection method of fluopicolide fungicide in a kind of grape wine according to claim 1, it is characterised in that：It is described
Eluting solvent in step 2 is ethyl acetate.
4. the detection method of fluopicolide fungicide in a kind of grape wine according to claim 1, it is characterised in that：It is described
The step of four in the detection parameters of gas chromatography tandem mass spectrometry instrument be：
Chromatographic column：HP-5MS, 30m × 0.25mm × 0.25 μm；
Temperature programming：1min is kept at 60 DEG C, then 200 DEG C are warming up to the speed of 30 DEG C of raising per minute, finally with per minute
The speed of 15 DEG C of raising is increased to 300 DEG C and keeps 5min；
Sample size：1μL；
Carrier gas：High-purity helium, purity >=99.999%, flow 1.0mL/min；
Collision gas：High-purity argon gas, purity >=99.999%；
Sample size mouth temperature：240℃；
Ion source：Chemical source uses the negative ion mode of NCI；Methane makees reaction gas, purity >=99.999%, flow 1.0mL/
min；Source temperature：200℃；
Interface temperature：250℃；
Scan pattern：MRM patterns.
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| CN201810083490.4A CN108152421A (en) | 2018-01-29 | 2018-01-29 | The detection method of fluopicolide fungicide in grape wine |
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| CN201810083490.4A CN108152421A (en) | 2018-01-29 | 2018-01-29 | The detection method of fluopicolide fungicide in grape wine |
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| CN109682897A (en) * | 2019-01-17 | 2019-04-26 | 南京大学 | A kind of method of a variety of incretion interferents in while determination of the environment water sample |
| CN111929376A (en) * | 2020-07-23 | 2020-11-13 | 河南科技学院 | Method for detecting methoxyl pyrazine compounds in wine |
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| CN111929376A (en) * | 2020-07-23 | 2020-11-13 | 河南科技学院 | Method for detecting methoxyl pyrazine compounds in wine |
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