CN103163266A - Method for determining pymetrozine residual quantity in tobacco by double column solid-phase extraction-liquid chromatography - Google Patents
Method for determining pymetrozine residual quantity in tobacco by double column solid-phase extraction-liquid chromatography Download PDFInfo
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Abstract
The invention provides a method for determining pymetrozine residual quantity in tobacco by double column solid-phase extraction-liquid chromatography. The method comprises the following steps of: (1) preparing standard solution, weighing a certain amount of pymetrozine standard substance, dissolving to constant volume by methanol, and preparing into pymetrozine standard stock solution, gradually diluting the pymetrozine standard stock solution, and preparing into a series of concentration standard work solution; (2) extracting, extracting the pymetrozine residue in the tobacco by methanol; (3) purifying by double column solid-phase extraction; (4) detecting by liquid chromatography; (5) building a standard curve; and (6) calculating and analyzing the pymetrozine residual quantity. The detection method disclosed by the invention has the characteristics of being simple, convenient, accurate, fast and reliable, and has important value on control of pymetrozine residue in the tobacco and guide of safe and reliable use of the pymetrozine in the tobacco.
Description
Technical field
The invention belongs to the Analytical Methods of Trace field, be specifically related to the residual method of pymetrozine in a kind of twin columns Solid-Phase Extraction-liquid chromatography for measuring tobacco.
Background technology
Pymetrozine belongs to pyridines or Triazinone pesticide, developed in 1988 by Switzerland Ciba-Geigy company the earliest, and be the brand-new non-insects agent of killing livestock, this product shows excellent prevention effect to the sucking pest of various crop.Pymetrozine to sucking pest particularly aphid, trialeurodes vaporariorum, rice green leafhopper have unique prevention effect, can be used for the control of multiple resistance strain insect.Because of its high selectivity that has, to mammiferous hypotoxicity with to birds, fish, the arthropodan security of non-target, demonstrate good development prospect in integrated control.Extensive application along with pymetrozine in agricultural production, its residue problem on environment and agricultural product also receives people's concern day by day.
Find through the literature search to prior art, present assay method about the pymetrozine residual quantity, it is generally the mixed solution that adopts acetonitrile, acetone and water, regulate the pH Acidity of Aikalinity, extract the pymetrozine residues of pesticides in paddy rice, vegetables, purify through dichloromethane extraction or chromatographic column, detect with gas chromatography-hydrogen flame detector (FID) or liquid chromatography.Detecting practice finds, although at present existing residue analysis method can guarantee extraction efficiency, but have the following disadvantages: 1) due to the mixed solution that adopts organic solvent and water as extraction agent, the impurity such as carbohydrate, fat, protein also easily are extracted, there is larger interference in detection to pymetrozine, although repeatedly extract with methylene chloride, has increased operation steps, not only increase workload, and easily caused error.2) need repeatedly to regulate pH in extraction and purification process, make extraction relative with purification process loaded down with trivial details.3) method that adopts column chromatography is complicated operation not only, and poor reproducibility, and is not suitable for the sample that tobacco contains a large amount of pigments, grease, impurity, and it is improper to purify, and impurity peaks is interference detection results very easily.
" modern " 12 phases in 2010 disclose the residue analysis method of a kind of pymetrozine in paddy rice, and it is to extract with acetonitrile and water mixed solution, through single SPE-C18 column purification, uses liquid chromatographic detection.The practice discovery, this residue analysis method has the following disadvantages: 1) in the removal tobacco, the impurity effect is relatively poor, and there are a large amount of impurity in tobacco sample in the peak, affects the accuracy of result judgement.2) minimal detectable concentration is higher, is unfavorable for the mensuration of low content pymetrozine.
" tobacco science and technology " the 5th phase in 2010 discloses pymetrozine content in a kind of high effective liquid chromatography for measuring dry tobacco leaf, and it is that acetonitrile is lotion repeatedly, passes through Pesticarb/NH with the ultrasonic extraction of acetonitrile
2Solid phase extraction column purifies, with the pre-drip washing of 10mL acetonitrile/toluene (V:V, 3:1), 30mL acetonitrile/toluene (V:V, 3:1) wash-out.This method is used for detecting the defective that in tobacco, the pymetrozine residual quantity exists: 1) be difficult to remove fully simultaneously for polarity and nonpolar two kinds of different impurities.2) not good enough for the extraction and cleaning effect of fresh tobacco leaf.3) adopt toluene as leacheate and eluent, consumption is large, and there is potential threat in strong toxicity to environment and human-body safety.
Due to the complicacy of tobacco sample itself, the existing method that detects the pymetrozine residual quantity is difficult to satisfy the needs to residue detection in tobacco, very easily causes departing from of result, the assessment that affects final testing result and pymetrozine is rationally used on tobacco.
Summary of the invention
The object of the invention is to make up the deficiency of existing pymetrozine detection technique, a kind of residual detection method of pymetrozine in tobacco that detects fast and accurately is provided.Easy, accurate, rapid, reliable characteristics that the method has, to control in tobacco pymetrozine residual, instruct the safe and reasonable of pymetrozine on tobacco to use to have important value.
The present invention is achieved by the following technical solutions:
The residual method of pymetrozine in a kind of twin columns Solid-Phase Extraction-liquid chromatography for measuring tobacco comprises the following steps::
(1) preparation of standard solution: take certain mass pymetrozine standard items, dissolve constant volume with methyl alcohol, make the pymetrozine standard reserving solution, with pymetrozine standard reserving solution stepwise dilution, be mixed with series concentration standard operation liquid;
(2) extract: take tobacco sample and be placed in conical flask, add 3～30 times of methyl alcohol of tobacco sample, filter after vibration, concentrated near doing;
(3) purify: residue water dissolving in concentrated bottle, change in the C18 solid phase pillar of methyl alcohol, the pre-drip washing of water the drip washing of methanol-water mixed solution, methanol-eluted fractions over to, collect eluent, concentrated, add methyl alcohol-methylene chloride mixed solution dissolving, change in the PSA solid phase pillar of methyl alcohol-pre-drip washing of methylene chloride mixed solution, methyl alcohol-methylene chloride mixed solution wash-out, collect efflux, concentrated, constant volume;
(4) detect: after instrument stabilizer, with the series concentration standard operation liquid sample introduction of step (1) preparation, retention time is qualitative, liquid chromatographic detection, and on this basis, the purification sample that step (3) is collected carries out liquid chromatographic detection;
(5) foundation of typical curve: take sample introduction concentration as horizontal ordinate, peak area is ordinate, the drawing standard curve;
(6) interpretation of result: the content that calculates as follows pymetrozine in sample
Pymetrozine residual quantity in the R-sample, the mg/kg of unit;
C
1-concentration of standard solution, the mg/L of unit;
V
1-standard solution sampling volume, the μ L of unit;
V
2The final constant volume of-sample solution, Unit/mL;
V
3-sample solution sampling volume, the μ L of unit;
S
1The peak height of-standard solution, AU;
S
2The peak height of-sample solution, AU;
The W-sample takes quality, the g of unit.
Further, the methanol-water mixed solution in described step (3) refers to that methyl alcohol and water volume ratio are the mixed solution of 5:95; Described methyl alcohol-methylene chloride mixed solution refers to that methyl alcohol and methylene chloride volume are than the mixed solution of 5:95.
Further, the liquid chromatographic detection in described step (4) adopts high performance liquid chromatograph-diode array detector (HPLC-DAD), Waters Alliance2695/2487, chromatographic column: Waters X-Brige, the C18 post, 5.0 μ m, 4.6 * 250mm; Testing conditions:
Mobile phase: acetonitrile/water solution, V:V are 15:85 to 80:20;
Flow velocity: 0.8ml/min;
Measure wavelength: 298nm;
Column temperature: 30 ℃;
Sample size: 10 μ L.
Further, the pymetrozine standard reserving solution in described step (3) refers to take 0.01g pymetrozine standard items, is settled to 100mL with the methyl alcohol dissolving, makes the 100mg/L storing solution.
Further, the series concentration standard operation liquid in described step (1) refer to 0.05,0.1,0.5,1.0,5.0, the pymetrozine typical curve working fluid of 10.0mg/L.
Further, the tobacco sample in described step (2) refers to a kind of in fresh tobacco leaf, dry tobacco leaf.
Further, the sample in described step (2) is placed in conical flask, refers to that 2～20g sample is placed in the 250mL conical flask.
Further, concentrating in described step (2) and (3) refers to will extract sample concentrated near doing in the scope of 40 ℃～50 ℃ with Rotary Evaporators.
The present invention adopts the twin columns Solid-Phase Extraction, and to impurity good purification in tobacco, accuracy in detection is high.
Compared with prior art, advantage of the present invention and good effect are:
The present invention adopts methyl alcohol as the pre-treatment step of extractant, and is simple, can effectively object be extracted in organic phase; Existing purifying step is improved, and twin columns purify impurity good purification in tobacco; The liquid chromatographic detection condition of optimizing, highly sensitive, accuracy good, can guarantee the needs of low concentration pymetrozine residue detection.
Description of drawings
Fig. 1 is the pymetrozine standard colors spectrogram of embodiment 1;
Fig. 2 is the fresh tobacco leaf blank sample chromatogram of embodiment 1;
Fig. 3 is the fresh tobacco leaf sample chromatogram figure of the interpolation pymetrozine of embodiment 1;
Fig. 4 is the dry tobacco leaf blank sample chromatogram of embodiment 2;
Fig. 5 is the dry tobacco leaf sample chromatogram figure of the interpolation pymetrozine of embodiment 2;
Wherein, in Fig. 1,3,5, the chromatographic peak of mark retention time represents pymetrozine.
Embodiment
The present invention is further detailed explanation below in conjunction with the drawings and specific embodiments.
The detection technique of the present invention for adopting liquid chromatography that the pymetrozine content in tobacco is detected.
Embodiment one: the detection of pymetrozine residual quantity in fresh tobacco leaf
1. extract
Take the 10.0g fresh tobacco leaf, add 60mL methyl alcohol, concussion 1h, Buchner funnel filters, and residue 20mL methanol wash is filtered, and 45 ℃ of concentrated filtrates are done near, add 2mL water, and are to be clean.
2. purify
The water-soluble solution residue of C18 column purification: 2mL.5mL methyl alcohol, the pre-drip washing of 5mL water.Upper prop.10mL methanol/water (5:95, v/v) drip washing discards.The 5mL methanol-eluted fractions is collected eluent.Concentrated near doing.
PSA column purification: 2mL ethanol/methylene (5:95, v/v) dissolved residue.The pre-drip washing PSA post of 10mL ethanol/methylene (1:99, v/v) discards.Upper prop is collected.12mL ethanol/methylene (5:95, v/v) wash-out is collected.Concentrated near doing adds the 2mL methanol constant volume, crosses 0.22 μ m mocromembrane and filters, and be to be measured.
3. liquid chromatographic detection
The liquid chromatographic detection condition is:
High performance liquid chromatograph-diode array detector (HPLC-DAD), Waters Alliance e2695/2998.
Chromatographic column: XBridge C18,5.0 μ m, 4.6 * 250mm.
Mobile phase: acetonitrile/water solution.
Column temperature: normal temperature.
Measure wavelength: 298nm.
Sample size: 10 μ L.
Condition of gradient elution such as following table:
The standard colors spectrogram of gained is seen Fig. 1 under these conditions.Retention time is 6.6min.
4. the foundation of typical curve
Take 0.0100g pymetrozine standard items, be settled to 100mL with the methyl alcohol dissolving, make the 100mg/L storing solution.With pymetrozine standard reserving solution stepwise dilution, be mixed with 0.05,0.1,0.5,1.0,5.0, the standard operation liquid of 10.0mg/L.Take sample introduction concentration as horizontal ordinate, peak area is ordinate, the drawing standard curve.Gained typical curve regression equation is: Y=70641X-720.86, coefficient R=1.0.
5. computing formula
Pymetrozine residual quantity (mg/kg) in the R-sample
C1-concentration of standard solution (mg/L)
V1-standard solution sampling volume (μ L)
The final constant volume of V2-sample solution (mL)
V3-sample solution sampling volume (μ L)
The peak height of S1-standard solution (AU)
The peak height of S2-sample solution (AU)
The W-sample takes quality (g)
6. interpolation recovery test
Add 0.01～1.0mg/kg pymetrozine standard solution in the fresh tobacco leaf blank sample, each concentration repeats 5 times, extracts as stated above, purifies and detect, the reliability of checking the inventive method.The results are shown in Table 1.
Table 1 pymetrozine adds the recovery test result in fresh tobacco leaf
Result shows, pymetrozine adds concentration when being 0.01mg/kg, 0.1mg/kg, 1.0mg/kg in fresh tobacco leaf, average recovery rate 93.2%～93.3%, relative standard deviation 0.7%～3.9%.The recovery and relative standard deviation all meet the requirement of residues of pesticides test.The chromatogram of pymetrozine in fresh tobacco leaf blank sample and interpolation sample seen Fig. 2 and Fig. 3.
As seen from Figure 2, clean-up effect of the present invention is good, inclusion-free almost in the fresh tobacco leaf blank sample.As seen from Figure 3, the pymetrozine peak shape is good, and the target peak place disturbs without other impurity peaks.
Embodiment two: the detection of pymetrozine residual quantity in dry tobacco leaf
1. extract
Take the 2.0g dry tobacco leaf, add 60mL methyl alcohol, 1h is extracted in concussion, and Filter paper filtering accurately measures 40mL, and 45 ℃ of concentrated near doing add 2mL water, and are to be clean.
2. purify
The water-soluble solution residue of C18 column purification: 2mL.5mL methyl alcohol, the pre-drip washing of 5mL water.Upper prop.10mL methanol/water (5:95, v/v) drip washing discards.The 5mL methanol-eluted fractions is collected eluent.Concentrated near doing.
PSA column purification: 2mL ethanol/methylene (5:95, v/v) dissolved residue.The pre-drip washing PSA post of 10mL ethanol/methylene (1:99, v/v) discards.Upper prop is collected.12mL ethanol/methylene (5:95, v/v) wash-out is collected.Concentrated near doing adds the 2mL methanol constant volume, crosses 0.22 μ m mocromembrane and filters, and be to be measured.
3. liquid chromatographic detection
The liquid chromatographic detection condition is:
High performance liquid chromatograph-diode array detector (HPLC-DAD), Waters Alliance e2695/2998.
Chromatographic column: XBridge C18,5.0 μ m, 4.6 * 250mm.
Mobile phase: acetonitrile/water solution.
Column temperature: normal temperature.
Measure wavelength: 298nm.
Sample size: 10 μ L.
Condition of gradient elution such as following table:
The standard colors spectrogram of gained is seen Fig. 1 under these conditions.Retention time is 6.6min.。
4. the foundation of typical curve
Take 0.0100g pymetrozine standard items, be settled to 100mL with the methyl alcohol dissolving, make the 100mg/L storing solution.With pymetrozine standard reserving solution stepwise dilution, be mixed with 0.05,0.1,0.5,1.0,5.0, the standard operation liquid of 10.0mg/L.Take sample introduction concentration as horizontal ordinate, peak area is ordinate, the drawing standard curve.Gained typical curve regression equation is: Y=70363X-1616.3, coefficient R=0.9999.
5. computing formula
Pymetrozine residual quantity (mg/kg) in the R-sample
C1-concentration of standard solution (mg/L)
V1-standard solution sampling volume (μ L)
The final constant volume of V2-sample solution (mL)
V3-sample solution sampling volume (μ L)
The peak height of S1-standard solution (AU)
The peak height of S2-sample solution (AU)
The W-sample takes quality (g)
6. interpolation recovery test
Add 0.02～1.0mg/kg pymetrozine standard solution in the dry tobacco leaf blank sample, each concentration repeats 5 times, extracts as stated above, purifies and detect, the reliability of checking the inventive method.The results are shown in Table 2.
Table 2 pymetrozine adds the recovery test result in dry tobacco leaf
Result shows, pymetrozine adds concentration when being 0.02mg/kg, 0.1mg/kg, 1.0mg/kg in fresh tobacco leaf, average recovery rate 89.0%～96.1%, relative standard deviation 0.7%～3.0%.The recovery and relative standard deviation all meet the requirement of residues of pesticides test.The chromatogram of pymetrozine in dry tobacco leaf blank sample and interpolation sample seen Fig. 4 and Fig. 5.
As seen from Figure 4, in the dry tobacco leaf blank sample, impurity is less, can not form interference to this experiment.As seen from Figure 5, near the pymetrozine target peak, inclusion-free disturbs, and can effectively improve Accuracy of Judgement as a result.
The above is only preferred embodiment of the present invention, is not to be the present invention to be done the restriction of other form, and any those skilled in the art may utilize the technology contents of above-mentioned announcement to be changed or be modified as the equivalent embodiment of equivalent variations.But every technical solution of the present invention content that do not break away to any simple modification, equivalent variations and remodeling that above embodiment does, still belongs to the protection domain of technical solution of the present invention according to technical spirit of the present invention.
Claims (8)
1. the residual method of pymetrozine in twin columns Solid-Phase Extraction-liquid chromatography for measuring tobacco is characterized in that comprising the following steps:
(1) preparation of standard solution: take certain mass pymetrozine standard items, dissolve constant volume with methyl alcohol, make the pymetrozine standard reserving solution, with pymetrozine standard reserving solution stepwise dilution, be mixed with series concentration standard operation liquid;
(2) extract: take tobacco sample and be placed in conical flask, add 3 ~ 30 times of methyl alcohol of tobacco sample, filter after vibration, concentrated near doing;
(3) purify: residue water dissolving in concentrated bottle, change in the C18 solid phase pillar of methyl alcohol, the pre-drip washing of water the drip washing of methanol-water mixed solution, methanol-eluted fractions over to, collect eluent, concentrated, add methyl alcohol-methylene chloride mixed solution again to dissolve, change in the PSA solid phase pillar of methyl alcohol-pre-drip washing of methylene chloride mixed solution, methyl alcohol-methylene chloride mixed solution wash-out, collect efflux, concentrated, constant volume;
(4) detect: after instrument stabilizer, with the series concentration standard operation liquid sample introduction of step (1) preparation, liquid chromatographic detection, on this basis, the purification sample that step (3) is collected carries out liquid chromatographic detection;
(5) foundation of typical curve: take sample introduction concentration as horizontal ordinate, peak area is ordinate, the drawing standard curve;
(6) interpretation of result: the content that calculates as follows pymetrozine in sample
R=
Pymetrozine residual quantity in R-sample, the mg/kg of unit;
C
1-concentration of standard solution, the mg/L of unit;
V
1-standard solution sampling volume, the μ L of unit;
V
2The final constant volume of-sample solution, Unit/mL;
V
3-sample solution sampling volume, the μ L of unit;
S
1The peak height of-standard solution, AU;
S
2The peak height of-sample solution, AU;
W-sample takes quality, the g of unit.
2. measure according to claim 1 the residual method of pymetrozine in tobacco, it is characterized in that: the methanol-water mixed solution in described step (3) refers to that methyl alcohol and water volume ratio are the mixed solution of 5:95; Described methyl alcohol-methylene chloride mixed solution refers to that methyl alcohol and methylene chloride volume are than the mixed solution of 5:95.
3. measure according to claim 1 the residual method of pymetrozine in tobacco, it is characterized in that: the liquid chromatographic detection in described step (4) adopts high performance liquid chromatograph-diode array detector, Waters Alliance 2695/2487, chromatographic column: Waters X-Brige, the C18 post, 5.0 μ m, 4.6 * 250 mm; Testing conditions:
Mobile phase: acetonitrile/water solution, V:V are 15:85 to 80:20;
Flow velocity: 0.8ml/min;
Measure wavelength: 298 nm;
Column temperature: 30 ℃;
Sample size: 10 μ L.
4. measure according to claim 1 the residual method of pymetrozine in tobacco, it is characterized in that: the pymetrozine standard reserving solution in described step (1), refer to take 0.01 g pymetrozine standard items, be settled to 100 mL with the methyl alcohol dissolving, make 100 mg/L storing solutions.
5. measure according to claim 1 the residual method of pymetrozine in tobacco, it is characterized in that: the series concentration standard operation liquid in described step (1) refers to the pymetrozine typical curve working fluid of 0.05,0.1,0.5,1.0,5.0,10.0 mg/L.
6. measure according to claim 1 the residual method of pymetrozine in tobacco, it is characterized in that: the tobacco sample in described step (2) refers to a kind of in fresh tobacco leaf, dry tobacco leaf.
7. measure according to claim 1 the residual method of pymetrozine in tobacco, it is characterized in that: the sample in described step (2) is placed in conical flask, refers to that 2 ~ 20 g samples are placed in 250 mL conical flasks.
8. measure according to claim 1 the residual method of pymetrozine in tobacco, it is characterized in that: concentrating in described step (2) and (3) refers to will extract sample concentrated near doing in the scope of 40 ℃ ~ 50 ℃ with Rotary Evaporators.
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