CN106442747B - A kind of method that chloropyuril in fruits and vegetables, 2,4-D, paclobutrazol residual quantity are measured simultaneously using gas chromatography mass spectrometry - Google Patents
A kind of method that chloropyuril in fruits and vegetables, 2,4-D, paclobutrazol residual quantity are measured simultaneously using gas chromatography mass spectrometry Download PDFInfo
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Abstract
The present invention discloses a kind of using gas chromatography mass spectrometry while measuring chloropyuril in fruits and vegetables, 2, the method of 4-D, paclobutrazol residual quantity, its method and step is as follows: step A prepares standard reserving solution, step B hybrid standard working solution, step C sample is extracted, step D purification, step E gas chromatography-mass spectrometry combination analysis, step F result calculates and analysis.The present invention disposably measures three kinds of chloropyuril, 2,4-D, paclobutrazol substances simultaneously, and operation detection is quick, the validity of detection is high, in 0.04-10ug/mL concentration range, linear good, the rate of recovery of method is in 85.7-95.9%, precision result RSD value is respectively less than 10.0%, meet experiment and daily detection requirement, using butyronitrile as extractant, impurity interference is few, the precision of measurement is higher, and it is good to measure repeatability.
Description
Technical field
It is specially a kind of same using gas chromatography mass spectrometry the present invention relates to fruits and vegetables residual chemicals detection technique field
When measurement fruits and vegetables in chloropyuril, 2,4-D, paclobutrazol residual quantity method.
Background technique
Salty plant growth regulator is the substance for coordinate plant growth, development, its application can ensure farming
Object stable yields improves quality of agricultural product, and can enhance the resistance of crop, makes agricultural production saving of work and time, cost-saving synergistic.At me
State's green cucumber registration allow using kind have Thidiazuron, chloropyuril, nucleotide, study on brassinolide, compound sodium nitrophenolate, naphthalene second
Acid, indolebutyric acid, 2,4- drop, paclobutrazol etc., main function are to promote female flower growth, improve percentage of fertile fruit, resist pest and disease damage etc.,
Middle chloropyuril is " swelling agent " being commonly called as, and chemical name is l- (the chloro- 4- pyridine of 2-) -3- phenylurea, has and promotes to bear fruit, makes
The effect of Fruit；It is widely used when the usual high concentration of 2,4- drops as a kind of effective herbicide, when low concentration
It is then planted as plant growth regulator for gourd, fruit and vegetable, protects flower rate, fruit retention rate to improve；Paclobutrazol is raw as a kind of plant
Long regulator can inhibit the biosynthesis of gibberellin, the supernutrition growth of plant be controlled, in favor of at flower, bearing fruit.With people
Living standard increasingly improve and the gradually attention to agricultural product organic production, also will to the safety of daily consumption food
It proposes requirements at the higher level, therefore establishes chloropyuril in a set of effective detection fruits and vegetables, 2,4- drop, the method for the residual quantity of paclobutrazol tool
There is social effect outstanding.
Summary of the invention
In view of the above-mentioned problems, the present invention provides it is a kind of using gas chromatography mass spectrometry simultaneously measure chloropyuril in fruits and vegetables,
2,4-D, the method for paclobutrazol residual quantity.
The technical solution adopted by the invention is as follows: it is a kind of using gas chromatography mass spectrometry simultaneously measure chloropyuril in fruits and vegetables,
2,4-D, the method for paclobutrazol residual quantity, preparation step are as follows:
Step A: preparing standard reserving solution, weighs appropriate standard items respectively, dense at following concentration: 2,4-D with acetone solution
Degree is 1000ug/mL, and chloropyuril concentration is 400ug/mL, and paclobutrazol concentration is 400ug/mL；
Step B: hybrid standard working solution pipettes the mixed mark work that each standard reserving solution prepares 3 kinds of titers in right amount respectively
Liquid series, the standard working solution series that dilution mixing standard liquid is 0.04-10 ug/mL；
Step C: sample extraction weighs and rubs homogeneous sample 10g in 50mL plastic centrifuge tube, and extractant, homogenate is added
After 2min, it is added sodium chloride and anhydrous magnesium sulfate, shake well is put into centrifuge centrifuge separation after standing, pipettes supernatant
5.0mL, with being dried with nitrogen, with 2mL acetone solution residue and obtains liquid to be clean in test tube；
Step D: purification, with the acetone of 5:95: n-hexane mixed liquor 5mL elutes florisil silica column in advance, discards；It will be to net
Change liquid and be transferred to pillar, and with the acetone of 5:95: n-hexane mixed liquor 10mL leacheate washs test tube several times, and is transferred to small
Column, collect leacheate, then the acetone with 30:70: n-hexane mixed liquor 10mL leacheate elutes pillar, merges leacheate, with rotation
It is close dry to turn cold boiler concentration, concentrate transfer is settled to 2 mL with acetone, through 0.45um membrane filtration and is obtained wait divide
Analyse liquid；
Step E: gas chromatography-mass spectrometry combination analysis, to the liquid to be analyzed for containing 2,4-D, chloropyuril, paclobutrazol
Chromatography and Mass Spectrometer Method analysis are carried out with series standard working solution；
Step F: result calculates and analysis, with the mass concentration of 2,4-D, chloropyuril, paclobutrazol for ordinate Y, with correspondence
Peak area be abscissa X, carry out linear regression drawing and obtain the linear equation of curve Y=KX, linear concentration range is
0.04-10ug/mL, according to 3 times of signal-to-noise ratio, actually to weigh sample 10.00g, 10mL acetonitrile is extracted, and takes 5.0mL extracting solution mistake
Florisil silica column, leacheate are finally settled to 2mL；Calculate detection limit, linear equation Y=KX, related coefficient K and detection limit.
In the above method of the invention, said extracted agent is the acetonitrile of 10.0mL, and above-mentioned sodium chloride is 1g, anhydrous slufuric acid
Magnesium is 5g.
In the above method of the invention, in above-mentioned gas chromatography-mass spectrometry combination analysis, chromatographic condition are as follows: color
Compose column: HP-5MS, 30m × 250um × 0.25um；Column temperature:, stopping 2min by 100 DEG C of initial temperature, rises to 180 DEG C with 10 DEG C/min, then
260 DEG C are risen to 5 DEG C/min, stops 2min, 280 DEG C of rear running temperature stops 5min；Injector temperature: 250 DEG C；Detector
Temperature: 280 DEG C；Carrier gas: high-purity helium, flow velocity 1.2mL/min；Sample volume: 2 μ L；It does not shunt.
In the above method of the invention, Mass Spectrometry Conditions are as follows: ion source temperature: 230 DEG C, transmission line temperature: 280 DEG C；Electricity
Son bombardment ionization source (EI), electron energy 70eV, Salbutamol Selected Ion Monitoring (SIM) mode, solvent delay 4.5min, 2,4-D with m/z
154 be quota ion, m/z 119, the 91 characteristic ion peaks m/z；Chloropyuril is quota ion, m/z 93, m/z with m/z 128
66 characteristic ion peaks；Paclobutrazol is quota ion, m/z 125, the 167 characteristic ion peaks m/z with m/z 236.
In the above method of the invention, X=c*V*V1/ (V2*m), in formula: X --- each chloropyuril in sample, 2,4-D,
The content of paclobutrazol, unit: mg；C --- chloropyuril, the mass concentration of 2,4-D, paclobutrazol in actual measurement sample, unit: ug/mL；
The volume of V1--- extractant, unit: mL；V2 --- point take extracting solution for purification volume, unit: mL；V --- purification
Constant volume after concentration, unit: mL；M --- the quality of sample is weighed, unit: g.
Beneficial effect
The present invention provide it is a kind of using gas chromatography mass spectrometry and meanwhile measure chloropyuril in fruits and vegetables, 2,4-D, paclobutrazol remain
The method of amount has the advantage that
1. of the invention disposably measure three kinds of chloropyuril, 2,4-D, paclobutrazol substances simultaneously, operation detection quickly, is once examined
A variety of different materials are surveyed, and the validity detected is high.
2. the present invention is in 0.04-10ug/mL concentration range, linear good, the rate of recovery of method is in 85.7-95.9%, essence
Density result RSD value is respectively less than 10.0%, meets experiment and daily detection requirement.
3. the present invention is extracted object using acetonitrile, object is reduced in water using sodium chloride and anhydrous magnesium sulfate
In solubility, promote the separation of acetonitrile layer and water, using florisil silica column except the impurity such as depigmentaton, reduce the dry of impurity
Disturb, effectively improve 2,4-D in fruits and vegetables, chloropyuril, paclobutrazol content measurement precision.
4. the present invention is good to the measurement repeatability of 2,4-D, chloropyuril, paclobutrazol, RSD value is respectively less than 10.0%.
5. the present invention is using mixing eluent, comprehensively considering eluent is first to be used again with 10mL5% acetone-n-hexane elution
10mL30% acetone-n-hexane elution, merges eluent twice, elutes better effect.
The present invention selects acetonitrile as extractant, and extraction recovery is preferable, and the impurity extracted is less.
Detailed description of the invention
Fig. 1 is the full scan mass spectrogram of 2,4-D.
Fig. 2 is the counting mass spectrogram of 2,4-D.
Fig. 3 is the relative abundance mass spectrogram of 2,4-D.
Fig. 4 is the full scan mass spectrogram of chloropyuril.
Fig. 5 is the counting mass spectrogram of chloropyuril.
Fig. 6 is the relative abundance mass spectrogram of chloropyuril.
Fig. 7 is the full scan mass spectrogram of paclobutrazol.
Fig. 8 is the counting mass spectrogram of paclobutrazol.
Fig. 9 is the relative abundance mass spectrogram of paclobutrazol.
Figure 10 is 2,4-D, chloropyuril, paclobutrazol standard chromatogram.
Figure 11 is that strawberry sample adds standard chromatogram.
Specific embodiment
In the following description, numerous specific details are set forth in order to facilitate a full understanding of the present invention.But the present invention can be with
Much it is different from other way described herein to implement, those skilled in the art can be without prejudice to intension of the present invention the case where
Under do similar popularization, therefore the present invention is not limited by the specific embodiments disclosed below.
Below with reference to embodiment, a specific embodiment of the invention is described further.
Embodiment 1
A kind of method that chloropyuril in fruits and vegetables, 2,4-D, paclobutrazol residual quantity are measured simultaneously using gas chromatography mass spectrometry,
Its preparation step is as follows:
Step A: preparing standard reserving solution, weighs appropriate standard items respectively, dense at following concentration: 2,4-D with acetone solution
Degree is 1000ug/mL, and chloropyuril concentration is 400ug/mL, and paclobutrazol concentration is 400ug/mL.
Step B: hybrid standard working solution pipettes the mixed mark work that each standard reserving solution prepares 3 kinds of titers in right amount respectively
Liquid series, the standard working solution series that dilution mixing standard liquid is 0.04-10 ug/mL.
Step C: sample extraction weighs and rubs homogeneous sample 10g in 50mL plastic centrifuge tube, and extractant, homogenate is added
After 2min, it is added sodium chloride and anhydrous magnesium sulfate, shake well is put into centrifuge centrifuge separation after standing, pipettes supernatant
5.0mL, with being dried with nitrogen, with 2mL acetone solution residue and obtains liquid to be clean in test tube.The extractant is 10.0mL's
Acetonitrile, the sodium chloride is 1g, anhydrous magnesium sulfate 5g.
Step D: purification, the acetone for being 5:95 with volume ratio: n-hexane mixed liquor 5mL elutes florisil silica column in advance, abandons
It goes；Liquid to be clean is transferred to pillar, and the acetone for being 5:95 with volume ratio: n-hexane mixed liquor 10mL leacheate is washed several times
Test tube is washed, and is transferred to pillar, collects leacheate, then the acetone for being 30:70 with volume ratio: n-hexane mixed liquor 10mL leacheate
Pillar is eluted, leacheate is merged, it is close dry with rotary vacuum evaporator concentration, concentrate transfer is settled to 2 mL with acetone, is passed through
0.45um membrane filtration simultaneously obtains liquid to be analyzed.
Step E: gas chromatography-mass spectrometry combination analysis, to the liquid to be analyzed for containing 2,4-D, chloropyuril, paclobutrazol
Chromatography and Mass Spectrometer Method analysis are carried out with series standard working solution.
Step F: result calculates and analysis, with the mass concentration of 2,4-D, chloropyuril, paclobutrazol for ordinate Y, with correspondence
Peak area be abscissa X, carry out linear regression drawing and draw the linear equation of curve Y=KX, linear concentration range is
0.04-10ug/mL, according to 3 times of signal-to-noise ratio, actually to weigh sample 10.00g, 10mL acetonitrile is extracted, and takes 5.0mL extracting solution mistake
Florisil silica column, leacheate are finally settled to 2mL；Calculate detection limit, linear equation, related coefficient K and detection limit.X=c*V*
V1/ (V2*m), in formula: X --- each chloropyuril, the content of 2,4-D, paclobutrazol, unit: mg in sample；C --- actual measurement sample
The mass concentration of middle chloropyuril, 2,4-D, paclobutrazol, unit: ug/mL；The volume of V1--- extractant, unit: mL； V2——
Point take extracting solution for purification volume, unit: mL；V --- constant volume after purification concentration, unit: mL；M --- it weighs
The quality of sample, unit: g.
In the gas chromatography-mass spectrometry combination analysis, chromatographic condition are as follows: chromatographic column: HP-5MS, 30m ×
250um×0.25um；Column temperature: 100 DEG C of initial temperature, 2min is stopped, rises to 180 DEG C with 10 DEG C/min, then rise to 260 with 5 DEG C/min
DEG C, 2min is stopped, 280 DEG C of rear running temperature stops 5min；Injector temperature: 250 DEG C；Detector temperature: 280 DEG C；Carrier gas:
High-purity helium, flow velocity 1.2mL/min；Sample volume: 2 μ L；It does not shunt；
In the gas chromatography-mass spectrometry combination analysis, Mass Spectrometry Conditions are as follows: ion source temperature: 230 DEG C, transmission line
Temperature: 280 DEG C；Electron impact ionization source (EI), electron energy 70eV, Salbutamol Selected Ion Monitoring (SIM) mode, solvent delay
4.5min, 2,4-D with m/z 154 be quota ion, m/z 119, the 91 characteristic ion peaks m/z；Chloropyuril is with m/z 128
Quota ion, m/z 93, the 66 characteristic ion peaks m/z；Paclobutrazol is quota ion, m/z 125, m/z 167 with m/z 236
Position characteristic ion peak.
Embodiment 2
In the present embodiment, experimental method in 1, specific experiment process are as follows in conjunction with the embodiments:
2.1 reagents and material
Unless otherwise indicated, all reagents are that analysis is pure, and water is tertiary effluent as defined in GB/T 6682.
Acetonitrile, n-hexane, acetone, ethyl acetate, chloropyuril, 2,4- drop, paclobutrazol standard items: Dr.Ehrenstorfer
It provides.
Chloropyuril, 2,4- drop, paclobutrazol standard solution:
Standard reserving solution: weighing appropriate standard items respectively, with acetone solution at following concentration: 2,4- drop concentration are
1000ug/mL, chloropyuril concentration are 400ug/mL, and paclobutrazol concentration is 400ug/mL.
Hybrid standard working solution: the mixed mark working solution series that each standard reserving solution prepares 3 kinds of titers in right amount is pipetted respectively.
The standard working solution series that dilution mixing standard liquid is 0.04-10 ug/mL.
Instrument and equipment
Gas chromatography-mass spectrometry: 7890/7000GC QQQ, Agilent company of the U.S..
Assay balance: sensibility reciprocal is 0.0001 g and 0.01 g.
Nitrogen evaporator.
Rotary vacuum evaporator
2.3 sample treatment
2.3.1 extracting
Weigh rubbing homogeneous sample 10g(and be accurate to 0.01g) in 50mL plastic centrifuge tube, it is accurate that 10.0mL second is added
Nitrile is separately added into 1g sodium chloride and 5g anhydrous magnesium sulfate after being homogenized 2min, shake well, and centrifuge centrifugation is put into after standing.It moves
Take supernatant 5.0mL in test tube, with being dried with nitrogen, with 2mL acetone solution residue, standby purification.
Purification
With 5mL acetone: n-hexane (5:95) elutes florisil silica column in advance, discards；Liquid to be clean is transferred to pillar, and
With 10mL acetone: n-hexane (5:95) leacheate washs test tube several times, and is transferred to pillar, collects leacheate, then use 10mL
Acetone: n-hexane (30:70) leacheate elutes pillar, merges leacheate, close dry with rotary vacuum evaporator concentration, will with acetone
Concentrate transfer is settled to 2 mL, through 0.45um membrane filtration, for analysis.
Instrumental conditions
2.4.1 chromatographic condition
Chromatographic column: HP-5MS, 30m × 250um × 0.25um；
Column temperature:, stopping 2min by 100 DEG C of initial temperature, rises to 180 DEG C with 10 DEG C/min, then rise to 260 DEG C with 5 DEG C/min, stops
2min, 280 DEG C of rear running temperature stop 5min；
Injector temperature: 250 DEG C；
Detector temperature: 280 DEG C；
Carrier gas: high-purity helium, flow velocity 1.2mL/min；
Sample volume: 2 μ L；It does not shunt.
Mass Spectrometry Conditions
Ion source temperature: 230 DEG C, transmission line temperature: 280 DEG C；Electron impact ionization source (EI), electron energy 70eV, choosing
Ion monitoring (SIM) mode, solvent delay 4.5min are selected, 2,4- drops are quota ion, m/z 119, m/z 91 with m/z 154
Characteristic ion peak；Chloropyuril is quota ion, m/z 93, the 66 characteristic ion peaks m/z with m/z 128；Paclobutrazol is with m/z
236 be quota ion, m/z 125, the 167 characteristic ion peaks m/z.
Embodiment 3
In conjunction with the embodiments 1 and embodiment 2, it experimental result discussion to embodiment 2 and is analyzed as follows:
The optimization of 3.1 chromatographic conditions
Grope to find that chloropyuril, 2,4- drop, paclobutrazol can be divided in DB-1701 and HP-5 chromatographic column by comparing
From, but on DB-1701, the peak shape of 2,4- drops has bulge, respond it is less than normal, comprehensively consider HP-5(30m × 250um ×
0.25um) separating effect is preferable, and peak shape is relatively preferable, and symmetry is good.
According to full scan determined respectively 2,4-D, chloropyuril, paclobutrazol selection fragment ion see Fig. 1-3, wherein 2,4-
Drop is base peak, m/z 119, the 91 characteristic ion peaks m/z with m/z 154；Chloropyuril is base peak, m/z 93, m/z with m/z 128
66 characteristic ion peaks；Paclobutrazol is base peak, m/z 125, the 167 characteristic ion peaks m/z with m/z 236.Hybrid standard chromatography
(SIM) and strawberry sample addition standard chromatogram is shown in Fig. 4, Fig. 5 respectively.
The optimization of sample pretreatment condition
3.2.1 the selection of extractant
Acetonitrile, acetone: the extraction effect of ethyl acetate (20:80) are compared, experimental result discovery is extracted back using acetonitrile
Yield is preferable, and the impurity extracted is less.Therefore select acetonitrile as extractant.
The selection of eluant, eluent
Compare 5% acetone-n-hexane, 10% acetone-n-hexane, 15% acetone-n-hexane, 20% acetone-n-hexane, 30%
Acetone-n-hexane elution effect, 2,4-D of discovery is best with 5% acetone-n-hexane elution effect, eluent dosage 10mL energy
98% or more 2,4-D is eluted, but it is unobvious to elute chloropyuril, the effect of paclobutrazol, and just with 10mL30% acetone-
Hexane can elute completely the two, and therefore, comprehensively considering eluent is first to be used again with 10mL5% acetone-n-hexane elution
10mL30% acetone-n-hexane elution, merges eluent twice.
Linear relationship and detection limit
With the mass concentration of 2,4-D, chloropyuril, paclobutrazol for ordinate, using corresponding peak area as abscissa, line is carried out
Property return, linear concentration range be 0.04-10ug/mL.According to 3 times of signal-to-noise ratio, actually to weigh sample 10.00g, 10mL acetonitrile
It extracts, takes 5.0mL extracting solution Florisil silica column, leacheate is finally settled to 2mL and calculates detection limit, linear equation, correlation
Coefficient and detection limit be shown in Table 1. seen from table 1 this method it is linearly good, detection limit meets 2,4-D in fruits and vegetables, chloropyuril, multiple-effect
The daily detection requirement of azoles.
1 standard curve linear equation of table and method detection limit
3.4 precision and the rate of recovery
It is operated by this experimental method, hybrid standard working solution is added in certain strawberry sample and carries out 6 parallel surveys respectively
Fixed, measuring 2,4-D in sample, chloropyuril, the relative standard deviation of paclobutrazol content and the rate of recovery the results are shown in Table 2.It can be with by table
Find out, 2,4-D, chloropyuril, the measurement repeatability of paclobutrazol it is good, RSD value is respectively less than 10.0%, and the rate of recovery is also in 85.7-
Between 95.9%.
2 precision of table and recovery test (n=6)
| Title | RSD(%) | Average recovery rate (%) |
| 2,4-D | 8.6 | 85.7 |
| Chloropyuril | 7.6 | 90.4 |
| Paclobutrazol | 4.3 | 95.9 |
The measurement of 3.5 actual samples
The assay that commercially available 10 kinds of freshs fruit of vegetables carry out 2,4-D, chloropyuril, paclobutrazol is had chosen, discovery result is such as
Table 3, the experimental results showed that having detection chloropyuril in strawberry and watermelon sample, swelling agent is widely used in such fruit of passing on a message in society
Chloropyuril, which has obtained part, to be confirmed, under normal operating condition, can be promoted fruit increase using chloropyuril, premature labor, be improved yield,
Phenomena such as will lead to fruit type deformity, dehiscent fruit is excessively used, proves chloropyuril to human health currently without specific scientific basis
Obvious harm is generated, the cell experiment that foreign countries once did shows that chloropyuril has an impact to the GTP assembling of mammalian cell, and animal is real
It tests and also indicates that, chloropyuril is used for a long time and has an impact to the kidney of rat, will lead to weight loss, have to skin, the eyes of rabbit
Minimal irritation.
2,4-D, chloropyuril, the content of paclobutrazol in 3 actual sample of table
| Title | 2,4-D(mg/kg) | Chloropyuril (mg/kg) | Paclobutrazol (mg/kg) |
| Strawberry | N.D | 0.22 | N.D |
| Watermelon | N.D | 0.12 | N.D |
| Kiwi berry | N.D | N.D | N.D |
| Pears | N.D | N.D | N.D |
| Apple | N.D | N.D | N.D |
| Cucumber | N.D | N.D | N.D |
| Spinach | N.D | N.D | N.D |
| Capsicum | N.D | N.D | N.D |
| Tomato | N.D | N.D | N.D |
| Cucurbita pepo | N.D | N.D | N.D |
4 conclusions
By verifying above, obtain this method in 0.04-10ug/mL concentration range, linear good, the rate of recovery of method
In 85.7-95.9%, precision result RSD value is respectively less than 10.0%, meets requirement of experiment, is mentioned object using acetonitrile in experiment
It takes out, reduces the solubility of object in water using sodium chloride and anhydrous magnesium sulfate, promote the separation of acetonitrile layer and water, benefit
The impurity such as depigmentaton are removed with florisil silica column, experiments have shown that this method 2,4-D, chloropyuril, paclobutrazol suitable for fruits and vegetables contain
The measurement of amount.
Although the present invention is disclosed as above with preferred embodiment, it is not for limiting the present invention, any this field skill
Art personnel without departing from the spirit and scope of the present invention, can make possible variation and modification, therefore guarantor of the invention
Shield range should be subject to the range that the claims in the present invention are defined.
Claims (5)
1. a kind of method that chloropyuril in fruits and vegetables, 2,4-D, paclobutrazol residual quantity are measured simultaneously using gas chromatography mass spectrometry,
Be characterized in that, preparation step is as follows: step A: preparing standard reserving solution, weighs appropriate standard items respectively, with acetone solution at
Following concentration: 2,4-D concentration are 1000ug/mL, and chloropyuril concentration is 400ug/mL, and paclobutrazol concentration is 400ug/mL；Step
B: hybrid standard working solution pipettes the mixed mark working solution series that each standard reserving solution prepares 3 kinds of titers in right amount respectively, and dilution is mixed
Close the standard working solution series that standard liquid is 0.04-10 ug/mL；Step C: sample extraction, weigh rub homogeneous sample 10g in
In 50mL plastic centrifuge tube, extractant is added, after being homogenized 2min, sodium chloride and anhydrous magnesium sulfate is added, shake well is stood
After be put into centrifuge centrifuge separation, pipette supernatant 5.0mL in test tube, with being dried with nitrogen, with 2mL acetone solution residue and
To liquid to be clean；Step D: purification, the acetone for being 5:95 with volume ratio: n-hexane mixed liquor 5mL elutes florisil silica column in advance,
It discards；Liquid to be clean is transferred to pillar, and the acetone for being 5:95 with volume ratio: n-hexane mixed liquor 10mL leacheate is several times
Test tube is washed, and is transferred to pillar, collects leacheate, then the acetone for being 30:70 with volume ratio: n-hexane mixed liquor 10mL elution
Liquid elutes pillar, merges leacheate, close dry with rotary vacuum evaporator concentration, and concentrate transfer is settled to 2 mL with acetone,
Through 0.45 μm of membrane filtration and obtain liquid to be analyzed；Step E: gas chromatography-mass spectrometry combination analysis, to containing 2,4-
D, chloropyuril, the liquid and series standard working solution to be analyzed progress chromatography of paclobutrazol and Mass Spectrometer Method analysis；Step F: result meter
It calculates and analyzes, with the mass concentration of 2,4-D, chloropyuril, paclobutrazol for ordinate Y, using corresponding peak area as abscissa X, into
Row linear regression charts and draws the linear equation of curve Y=KX, and linear concentration range is 0.04- 10ug/mL, according to signal-to-noise ratio
3 times, actually to weigh sample 10.00g, 10mL acetonitrile is extracted, and takes 5.0mL extracting solution Florisil silica column, leacheate is final
It is settled to 2mL；Calculate detection limit, linear equation, related coefficient K and detection limit；Wherein ug/mL is mcg/ml.
2. a kind of chloropyuril in fruits and vegetables, 2,4-D, more of being measured simultaneously using gas chromatography mass spectrometry according to claim 1
The method for imitating azoles residual quantity, which is characterized in that the extractant is the acetonitrile of 10.0mL, and the sodium chloride is 1g, anhydrous slufuric acid
Magnesium is 5g.
3. a kind of chloropyuril in fruits and vegetables, 2,4-D, more of being measured simultaneously using gas chromatography mass spectrometry according to claim 1
The method for imitating azoles residual quantity, which is characterized in that in the gas chromatography-mass spectrometry combination analysis, chromatographic condition are as follows: color
Compose column: HP-5MS, 30m × 250um × 0.25um；Column temperature:, stopping 2min by 100 DEG C of initial temperature, rises to 180 DEG C with 10 DEG C/min, then
260 DEG C are risen to 5 DEG C/min, stops 2min, 280 DEG C of rear running temperature stops 5min；Injector temperature: 250 DEG C；Detector
Temperature: 280 DEG C；Carrier gas: high-purity helium, flow velocity 1.2mL/min；Sample volume: 2 μ L；It does not shunt.
4. a kind of chloropyuril in fruits and vegetables, 2,4-D, more of being measured simultaneously using gas chromatography mass spectrometry according to claim 1
The method for imitating azoles residual quantity, which is characterized in that in the gas chromatography-mass spectrometry combination analysis, Mass Spectrometry Conditions are as follows: from
Source temperature: 230 DEG C, transmission line temperature: 280 DEG C；Electron impact ionization source (EI), electron energy 70eV, Salbutamol Selected Ion Monitoring
(SIM) mode, solvent delay 4.5min, 2,4-D with m/z 154 be quota ion, and m/z 119, m/z 91 are characterized quasi-molecular ions；
Chloropyuril is quota ion with m/z 128, and m/z 93, m/z 66 are characterized quasi-molecular ions；Paclobutrazol with m/z 236 be it is quantitative from
Son, m/z 125, the 167 characteristic ion peaks m/z.
5. a kind of chloropyuril in fruits and vegetables, 2,4-D, more of being measured simultaneously using gas chromatography mass spectrometry according to claim 1
The method for imitating azoles residual quantity, which is characterized in that X=c*V*V1/ (V2*m), in formula: X --- each chloropyuril in sample, 2,4-D,
The content of paclobutrazol, unit: mg；C --- chloropyuril, the mass concentration of 2,4-D, paclobutrazol in actual measurement sample, unit: ug/mL；
The volume of V1--- extractant, unit: mL；V2 --- point take extracting solution for purification volume, unit: mL；V --- purification
Constant volume after concentration, unit: mL；M --- the quality of sample is weighed, unit: g.
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