CN105223278B - Metalaxyl, the method for carbendazim in SPE HPLC/MS-MS grape wine - Google Patents
Metalaxyl, the method for carbendazim in SPE HPLC/MS-MS grape wine Download PDFInfo
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- CN105223278B CN105223278B CN201410228552.8A CN201410228552A CN105223278B CN 105223278 B CN105223278 B CN 105223278B CN 201410228552 A CN201410228552 A CN 201410228552A CN 105223278 B CN105223278 B CN 105223278B
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Abstract
The invention discloses a kind of method of metalaxyl, carbendazim in SPE HPLC/MS-MS grape wine, pH value including first adjusting grape wine to be measured, liquid-liquid extraction is carried out to wine sample with acetonitrile, add sodium chloride and SPE column extracting acetonitrile layer is used after solution is saltoutd, eluted by solid-phase extraction column, eluent after collection and purification, then it is transferred to Rotary Evaporators concentration, concentrate is dried up with nitrogen, after acetonitrile solution back dissolving, injection LC-MS instrument is analyzed, that is, the step of obtaining metalaxyl, the content of carbendazim in grape wine.This method has the outstanding advantages such as consumption of organic solvent is few, rate of extraction is fast, impurity is disturbed less, sample recovery rate height, and the control and risk management that effective chemistry security limitation can be set up for grape wine provide technical support.
Description
Technical field
The present invention relates to product safety and detection technique field, and in particular to a kind of SPE Liquid Chromatography/Mass Spectrometry detects Portugal
The residual method of grape wine middle peasant.
Background technology
Grape wine is made after new fresh grape or grape juice fermentation, rich in a variety of nutrients in grape wine, such as amino acid,
Vitamin, cupreol, polyphenol and mineral element etc., health can be strengthened with prevention disease by suitably drinking grape wine.But
During the prevention and control of plant diseases, pest control of grape, the agricultural chemicals such as insecticide, bactericide and herbicide are often sprayed.In general, agricultural chemicals
The longevity of residure is long, and with certain toxicity, the agricultural chemicals so remained can eventually enter into human body by food chain, strong to human body
Health is brought potentially hazardous.
With detection technique and the raising of Safety of Food Quality requirement, the report residual to grape wine middle peasant increasingly increases within nearly 2 years
It is many.And grape commonly uses the agricultural chemicals such as carbendazim, metalaxyl in the anti-evil of disease pest, wherein, carbendazim (Carbendazim, MBC),
Chemical name is N- (2- benzimidazolyls) carbamate, is a kind of wide spectrum, interior adsorptivity bactericide, can effectively prevent Portugal
Grape white rot, anthrachose of grape, anthracnose etc..Metalaxyl (metalaxyl), belongs to phenylamide high-efficiency low-toxicity systemic fungicide,
Chemical name：D, L-N- (2,6 3,5-dimethylphenyl)-N- (2'- methoxy ethyls) aminopropanoate, is mainly used in grape wine
The preventing and treating of Pseudoperonospora cubensis, phytophthora germ and maize ear rot bacterium, but both agricultural chemicals have carcinogenic to human body or cause genetic disease wind
Danger, so metalaxyl, carbendazim feasibility detection method in research grape wine, to safeguarding domestic and international Grape Wine Industry specification and being good for
Kang Fazhan has realistic meaning.
At present for grape wine middle peasant it is residual-the residual item detection of agriculture such as metalaxyl, carbendazim marks without specific country's detection
Report relates generally to gas chromatography, high performance liquid chromatography, gas chromatography/gas chromatography mass spectrometry in accurate or Patents, document
Method, liquid chromatography/mass spectrometry combination analysis method etc., pre-treating method mainly use liquid/liquid extraction (Liquid/liquid
Extraction, LLE), accelerated solvent extraction (Accelerate solvent extraction, ASE), SPME
(Solid phase microextration, SPME) and SPE column extracting (Solidphase extration, SPE)
Deng, but wine samples composition is miscellaneous, matrix interference big, if pre-treatment is improper, easily influences testing result.
The content of the invention
Problem to be solved by this invention is to provide metalaxyl, carbendazim in SPE HPLC/MS-MS grape wine
The quantitative approach of content, its analysis process includes the preprocess method of sample and the detection method of target compound, it is adaptable to Portugal
The residual detection of related agriculture in grape wine, its result can control to provide reference for the threshold limit values of carbendazim in grape wine, metalaxyl.
In order to solve foregoing technical problem, the present invention, which provides technical scheme, is：
Metalaxyl, the method for carbendazim, comprise the following steps in a kind of SPE HPLC/MS-MS grape wine：
(1) carbendazim, the standard curve of metalaxyl are drawn
A. gradient standard serial solution is made with carbendazim, metalaxyl standard liquid respectively,
B. each solution ph in regulating step A, liquid-liquid extraction is carried out with acetonitrile,
C. sodium chloride is added, after solution saltouts layering, acetonitrile layer is extracted with amino solid-phase extraction column, using washing
De- liquid is eluted to solid-phase extraction column, collects eluent, is dried up after being transferred to Rotary Evaporators concentration with nitrogen,
D. by acetonitrile solution back dissolving after, injection LC-MS instrument analyzed, acquisition grape wine in metalaxyl, many bacterium
The content of spirit,
E. by the concentration of target compound to chromatographic peak area correspondence, that is, the standard curve after being calibrated；
(2) using wine samples to be measured as sample, using the method for A-E in step (1), grape wine sample to be measured can be obtained
Sample measurements in product, after the measured value reference standard curve, can calculate and obtain carbendazim and metalaxyl in grape wine and contain
Amount.
It is preferred that technical scheme be：In step (1) B, testing sample acid-base value is adjusted using 0.5mol/L sodium hydroxides：Adjust
Save pH=8.
It is preferred that technical scheme be：In step (1) C, using amino SPE column extracting, its elution requirement is：Toluene：
Acetonitrile=3:1, eluting agent 15mL, are eluted in three times.
It is preferred that technical scheme be：In step (1) D, back dissolving is carried out using 80% acetonitrile solution.
It is preferred that technical scheme be：In step (1) D, condition determination is：Chromatographic column：Inertsil C8,5 μm, 150mm*
2.1 (internal diameters) or quite person.Mobile phase is acetonitrile solution (B) gradient elution of 0.3% acetic acid aqueous solution (A) and 0.3% acetic acid,
Column temperature：30℃.
It is preferred that technical scheme be：In step (1) D, after eluent is dried up through nitrogen, 1mL, 80% aqueous acetonitrile are dissolved in
In liquid, 20 μ L solution feed liquor matter combined instruments are taken to be analyzed.
The present invention considers selected target compound carbendazim (carbendazim, CAS No.10605-21-7), first frost
The chemical property and aqueous phase, the difference of oil phase affinity of clever (Metalaxyl, CAS No.57837-19-1), are developed a kind of suitable
Close the analysis method of the residual detection of grape wine middle peasant：Wine sample pH value is first adjusted, liquid-liquid extraction is carried out to wine sample with acetonitrile, chlorination is added
After sodium salt analysis layering, take acetonitrile layer by SPE column purification, rotary evaporation, nitrogen are enriched with object after blowing, and pass through acetonitrile water
After solution back dissolving, target compound is detected with liquid chromatogram-quadrupole rod tandem mass spectrum combined instrument (LC-MS).
Relative to prior art, it is an advantage of the invention that：
1. technical solution of the present invention establishes suitable grape wine middle peasant error term mesh metalaxyl, the abstraction technique of carbendazim detection
Program, i.e., carried out the qualitative and quantitative analysis of target compound by liquid chromatogram-quadrupole rod tandem mass spectrum combined instrument, be applicable to Portugal
The assay of target compound in grape wine sample.
2. this method has, high sensitivity, consumption of organic solvent are few, rate of extraction is fast, impurity is disturbed less, sample recovery rate
High outstanding advantages, the control and risk management that effective chemistry security limitation can be set up as grape wine provides technical support.
3. this method can effectively overcome during grape wine is detected the factors such as complicated component, matrix interference be big, while determinand is net
Change fully, the rate of recovery it is high, disclosure satisfy that high flux, highly sensitive quick detection demand.
Brief description of the drawings：
Below in conjunction with the accompanying drawings and embodiment the invention will be further described：
Figure 1A is metalaxyl chromatographic peak area to the standard curve y=2.05e+006x+1.77e+005 of concentration, phase relation
Number γ=0.9992 (0.0~5.0 μ g/L)；
Figure 1B is carbendazim chromatographic peak area to the standard curve y=2.68e+006x+6.56e+004 of concentration, phase relation
Number γ=0.9993 (0.0~5.0 μ g/L)；
Fig. 2 is the constitutional diagram of collection standard specimen under positive ion mode；2A is metalaxyl, carbendazim standard specimen spectrogram, and 2B is first frost
Clever standard specimen spectrogram, 2C is carbendazim standard specimen spectrogram.
Fig. 3 is prepare liquid total ion current figure.3A is metalaxyl, carbendazim spectrogram in wine sample to be measured, and 3B is in wine sample to be measured
Metalaxyl spectrogram, 3C is carbendazim spectrogram in wine sample to be measured.
Embodiment：
Such scheme is described further below in conjunction with specific embodiment.It should be understood that these embodiments are to be used to illustrate
The invention is not restricted to limit the scope of the present invention.The implementation condition used in embodiment can be done according to the condition of specific producer into
One successive step, unreceipted implementation condition is usually the condition in normal experiment.
Embodiment：SPE liquid chromatogram-quadrupole rod tandem mass spectrum combined instrument determines carbendazim, first in claret
The technique study of white spirit content.
1 material and method
1.1 instruments and reagent：
4500 ultra performance liquid chromatographies of API TripleQuad-series connection quadrupole rod GC-MS (AB SCIEX companies),
XS105 balances (Mettler Toledo), NH2 solid-phase extraction columns (1g/6ml, waters companies of the U.S.).
Carbendazim (carbendazim, CAS No.10605-21-7, standard items), metalaxyl (Metalaxyl, CAS
No.57837-19-1, standard items), acetonitrile (Acetonitrile, HPLC grades), sodium chloride (Sodium chloride, GR grade),
Toluene (Methylbenzene, HPLC grades), the self-control of distilled water laboratory.
1.2 instrument condition
Ultra performance liquid chromatography-series connection quadrupole rod GC-MS condition determination is：Chromatographic column：Inertsil C8,5 μm,
150mm*2.1 (internal diameter)；Mobile phase is acetonitrile solution (B) gradient elution of 0.3% acetic acid aqueous solution (A) and 0.3% acetic acid：
0.00min, A:B=95:5；2.00min, A:B=50:50；5.00min, A:B=10:90；13.00min, A:B=10:90；
13.01min, A:B=95:5；15.00min, A:B=95:5；Column temperature：30℃.
The chromatogram condition of gradient elution of table 1
| Time/min | Flow velocity/(mL/min) | 0.3% acetic acid aqueous solution/(%) | The acetonitrile solution of 0.3% acetic acid/(%) |
| 00:00:01 | 0.25 | 95 | 5 |
| 00:02:00 | 0.25 | 50 | 50 |
| 00:05:00 | 0.25 | 10 | 90 |
| 00:13:00 | 0.25 | 10 | 90 |
| 00:13:01 | 0.25 | 95 | 5 |
| 00:15:00 | 0.25 | 95 | 5 |
1.3 analyses are determined
1.3.1 sample extraction
2.0000g samples (being accurate to 1mg) accurately are weighed in 10mL color-comparison tubes, are adjusted with 0.5mol/L sodium hydroxides
Testing sample pH to 7.5 is saved, 8mL acetonitrile whirlpools 1min is added and mixes, plus 3g sodium chloride, whirlpool 1min is mixed, in 4500r/
Min, centrifuges 5min, after layering, Aspirate supernatant 4mL is to be clean.
1.3.2 sample purification
2.5g anhydrous sodium sulfates are added in NH2 solid-phase extraction columns, first prewashing post are carried out with 5mL toluene+acetonitrile (3+1),
When liquid level is reached at the top of sodium sulphate, liquid to be clean in 1.3.1 is subjected to SPE, and received with 15mL tool plug pipes, then
Sample bottle is washed with 5mL toluene+acetonitrile (3+1) respectively 3 times, then cleaning solution is moved into solid-phase extraction column, merge sample in tool plug pipe
Liquid, and under 45 DEG C of water bath conditions, rotary evaporation is concentrated into about 0.5ml.Concentrate is placed on nitrogen evaporator, 45 DEG C of water bath conditions
Lower nitrogen, which is blown to, closely to be done, and is rapidly added 80% acetonitrile solution back dissolving, ultrasound is mixed, after 0.22 μm of organic membrane filtration, is carried out
Liquid chromatography tandom mass spectrometry determination.
1.3.3 the foundation of calibration curve
The drafting of calibration curve：By matrix with mark, prepared by carbendazim, metalaxyl standard reserving solution according to 7 point calibrations
0.000~5.0 μ g/L, obtain the linear relationship of the concentration correspondence response (peak area) of target compound.
Standard curve is with the concentration (μ g/L) of target compound to be measured for abscissa, and measured value (peak area) is ordinate system
Make standard curve, Figure 1A is standard curve (y=2.05e+006x+1.77e+005, r=of the metalaxyl chromatographic peak area to concentration
0.9992), (0.0~5.0 μ g/L)；Figure 1B is standard curve (y=2.68e+006x+ of the carbendazim chromatographic peak area to concentration
6.56e+004, r=0.9993), (0.0~5.0 μ g/L).
1.3.4 Mass Spectrometry Conditions
Ion gun：EI sources；
Scan pattern：Multiple-reaction monitoring；
What is optimized goes cluster voltage and collision energy parameter as shown in the table：
The mass spectrum acquisition parameter of table 2
1.3.5 the measure of sample recovery of standard addition
Preparation standard curve is carried out using matrix mark-on in experimentation, it is artificial to control whether to have in whole experiment process
Or the pollution that environmental factor is brought, the accuracy of confirmatory experiment process.With concentration 0.2 μ g/L, 0.4 μ g/L, 2.0 μ g/L target
Compound prepares standard sample, carries out rate of recovery experiment, separately does blank assay with same matrix sample, measurement result is：Many bacterium
Clever blank recovery of standard addition 60~90%, RSD be 2.2~12.6%, metalaxyl blank recovery of standard addition 80~105%,
RSD is 2.0~8.2%.
2 results are with discussing
If Fig. 2 is component that standard specimen is gathered under positive ion mode, Fig. 3 is prepare liquid total ion current figure.
The determination of 2.1 testing sample pH conditions
Carbendazim, metalaxyl blank recovery of standard addition measurement result under condition of different pH in the claret of table 3
The present embodiment has been investigated to carbendazim, the effect of extracting of metalaxyl under condition of different pH, as shown in Table 3, in pH=
When 8.0, the carbendazim rate of recovery is up to 80.2% in institute's test sample product, and the rate of recovery of metalaxyl is up to 94.1%, and the rate of recovery is stable, can
Meet the detection demand of carbendazim in grape wine, metalaxyl.Therefore, the present embodiment is used as first frost in grape wine from pH=8.0
Spirit, the pre-treatment acid-base value regulation of carbendazim detection.
2.2 extractants it is selected
The present embodiment first adjusts wine sample pH=8.0, then investigates n-hexane, ethyl acetate, three kinds of extractants pair of acetonitrile
Carbendazim, the influence of the effect of extracting of metalaxyl in grape wine.
The test result of the different solid extracting agents of table 4
From table 4, from acetonitrile extraction, target component average recovery rate is superior to ethyl acetate, n-hexane.Therefore,
The present embodiment is used as extractant from acetonitrile.
2.3 solid-phase extraction columns compare
Amino solid-phase extraction column and graphitized carbon/two kinds of amino composite solid-phase extraction column solid-phase extraction column pair have been investigated respectively
Metalaxyl, carbendazim, the effect of extracting of metalaxyl.
The test result of the different solid-phase extraction columns of table 5
Ketjenblack EC is going to be better than amino solid-phase extraction column on the impurity such as depigmentation, but has certain absorption to object
Effect；Sample is enough to remove the impurity such as the pigment of wine sample to be measured after acetonitrile extraction with amino solid-phase extraction column, can by table 5
See, amino solid-phase extraction column effect of extracting is better than graphitized carbon/amino composite solid-phase extraction column.Therefore, the present embodiment selects ammonia
Base solid-phase extraction column.
3 conclusions
3.1 sample extraction
The present embodiment takes 2.0000g wine sample (being accurate to 1mg) using carbendazim, metalaxyl as target compound, uses
0.5mol/L sodium hydroxides adjust pH to 8.0, add after 8mL acetonitrile whirlpools 1min mixings, plus 2.0g sodium chloride, and whirlpool is mixed,
In 4500r/min, 5min is centrifuged, after after solution layering, Aspirate supernatant 4mL is to be clean.
3.2 sample purification
2.5g anhydrous sodium sulfates are added in NH2 solid-phase extraction columns, first prewashing post are carried out with 5mL toluene+acetonitrile (3+1),
When liquid level is reached at the top of anhydrous sodium sulfate, liquid to be clean in 3.1 is subjected to SPE, and received with 15mL tool plug pipes, so
Wash with 5mL toluene+acetonitrile (3+1) sample bottle respectively afterwards 3 times, then cleaning solution is moved into solid-phase extraction column, merge and collect in tool
The sample liquid in pipe is filled in, and under 45 DEG C of water bath conditions, rotary evaporation is concentrated into about 0.5ml.Concentrate is placed on nitrogen evaporator, 45
Nitrogen is blown near dry under DEG C water bath condition, is rapidly added 80% acetonitrile solution back dissolving, ultrasound is mixed, through 0.22 μm of organic filter membrane mistake
After filter, take 20 μ L prepare liquids to inject liquid chromatography-tandem mass spectrometry instrument and determine.This method is to carbendazim blank recovery of standard addition 60
~90%, RSD are 2.2~12.6%, and metalaxyl blank recovery of standard addition is 2.0~8.2% in 80~105%, RSD.Can pin
The residual carbendazim of grape wine middle peasant, metalaxyl experiment safety limitation are evaluated with product safety.
The foregoing examples are merely illustrative of the technical concept and features of the invention, its object is to allow person skilled in the art's energy
Solution present disclosure much of that is simultaneously implemented according to this, and it is not intended to limit the scope of the present invention.It is all spiritual according to the present invention
Equivalent transformation or modification that essence is done, should all be included within the scope of the present invention.
Claims (6)
1. metalaxyl, the method for carbendazim, comprise the following steps in a kind of SPE HPLC/MS-MS grape wine：
(1) metalaxyl, the standard curve of carbendazim are drawn
A. gradient standard serial solution is made with metalaxyl, carbendazim solution respectively,
B. each solution ph in regulating step A, liquid-liquid extraction is carried out with acetonitrile,
C. sodium chloride is added, after solution saltouts layering, acetonitrile layer is extracted with amino solid-phase extraction column, eluent is utilized
Solid-phase extraction column is eluted, eluent is collected, is dried up after being transferred to Rotary Evaporators concentration with nitrogen,
D. by acetonitrile solution back dissolving after, injection LC-MS instrument is analyzed, metalaxyl, carbendazim in acquisition grape wine
Content, ultra performance liquid chromatography-series connection quadrupole rod GC-MS condition determination is：Chromatographic column：Inertsil C8,5 μm,
150mm*2.1 internal diameter；Mobile phase is acetonitrile solution (B) gradient elution of 0.3% acetic acid aqueous solution (A) and 0.3% acetic acid：
0.00min, A:B=95:5；2.00min, A:B=50:50；5.00min, A:B=10:90；13.00min, A:B=10:90；
13.01min, A:B=95:5；15.00min, A:B=95:5；Column temperature：30℃；
E. by the concentration of target compound to chromatographic peak area correspondence, that is, the standard curve after being calibrated；
(2) using wine samples to be measured as sample, using the method for A-E in step (1), the sample in wine samples to be measured is obtained
Product measured value, after the measured value reference standard curve, calculating obtains carbendazim and metalaxyl content in grape wine.
2. according to the method described in claim 1, it is characterised in that in step (1) B, using 0.5mol/L sodium hydroxides
Testing sample acid-base value is adjusted, pH=8.0 is adjusted.
3. according to the method described in claim 1, it is characterised in that in step (1) C, extracted using amino solid-phase extraction column
Take, its elution requirement is：Toluene：Acetonitrile=3:1, eluting agent 15mL, are eluted in three times.
4. according to the method described in claim 1, it is characterised in that in step (1) D, using 80% acetonitrile solution
Carry out back dissolving.
5. according to the method described in claim 1, it is characterised in that molten after eluent is dried up with nitrogen in step (1) D
Solution takes 20 μ L solution feed liquor matter combined instruments to be analyzed in the aqueous solution of the acetonitriles of 1mL 80%.
6. according to the method described in claim 1, it is characterised in that described step (1) and (2) sequencing is interchangeable.
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| CN106596776B (en) * | 2016-12-20 | 2019-06-07 | 鹿泽启 | The pre-treating method of pyrethroid pesticide remained test sample in grape wine |
| CN107478737B (en) * | 2017-07-18 | 2021-05-04 | 贵州茅台酒股份有限公司 | Method for detecting residual quantity of 80 pesticides in white spirit |
| CN107478496A (en) * | 2017-08-24 | 2017-12-15 | 山东省城市供排水水质监测中心 | The extraction detection method of organophosphor in a kind of water |
| CN109633026A (en) * | 2019-01-03 | 2019-04-16 | 上海市农业科学院 | A kind of method that liquid chromatography-tandem mass spectrometry detects carbendazim and its metabolin |
| CN115112804B (en) * | 2022-07-28 | 2023-11-21 | 宜宾五粮液股份有限公司 | Method for detecting sterols in white spirit |
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| CN1959406A (en) * | 2006-11-03 | 2007-05-09 | 南通市农产品质量检验测试中心 | Method for detecting residue of Metalaxyl, badistan, thiophanate-methyl in vegetable |
| CN102735784A (en) * | 2011-04-11 | 2012-10-17 | 中国科学院长春应用化学研究所 | Method for simultaneously determining one hundred pesticide residuals in traditional Chinese medicine through ultrahigh performance liquid chromatography-tandem quadrupole mass spectrum |
| CN103698462A (en) * | 2014-01-06 | 2014-04-02 | 中国烟草总公司郑州烟草研究院 | Method for detecting plurality of residual pesticides in tobacco simultaneously |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1959406A (en) * | 2006-11-03 | 2007-05-09 | 南通市农产品质量检验测试中心 | Method for detecting residue of Metalaxyl, badistan, thiophanate-methyl in vegetable |
| CN102735784A (en) * | 2011-04-11 | 2012-10-17 | 中国科学院长春应用化学研究所 | Method for simultaneously determining one hundred pesticide residuals in traditional Chinese medicine through ultrahigh performance liquid chromatography-tandem quadrupole mass spectrum |
| CN103698462A (en) * | 2014-01-06 | 2014-04-02 | 中国烟草总公司郑州烟草研究院 | Method for detecting plurality of residual pesticides in tobacco simultaneously |
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