CN105241981B - A kind of method for determining Pesticide Residues in Tea amount - Google Patents
A kind of method for determining Pesticide Residues in Tea amount Download PDFInfo
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- CN105241981B CN105241981B CN201510822373.1A CN201510822373A CN105241981B CN 105241981 B CN105241981 B CN 105241981B CN 201510822373 A CN201510822373 A CN 201510822373A CN 105241981 B CN105241981 B CN 105241981B
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Abstract
A kind of method for determining Pesticide Residues in Tea amount, comprises the following steps：(1) sample pre-treatments：After tealeaves is crushed, after being dissolved with water, with acetonitrile and acetone solution ultrasonic extraction, extract is obtained after centrifugation；(2) stirring rod SPE：It is coated with the stirring rod of polymer graphite ene coatings and immerses to carry out SPE into above-mentioned extract；(3) gaschromatographic mass spectrometry is detected, wherein, residues of pesticides remain for triazole pesticide；Polymer graphite ene coatings in stirring rod are specially chitosan graphite ene coatings.The application can be realized efficiently, detected easily to Pesticide Residues in Tea amount.
Description
Technical field
Gas chromatography-mass spectrum is utilized to triazole in tealeaves the invention belongs to technical field of analysis and detection, more particularly to one kind
The method that pesticide residue amount is checked.
Background technology
Triazole pesticide is organic heterocyclic class compound, has sterilization and the effect of coordinate plant growth concurrently.Some triazole types
Compound can strongly suppress the formation of ergosterol in pathogen body, show strong bactericidal action, and adjust with plant growth
Section is acted on；Some triazole class compounds can prevent the formation of auxin and gibberellin in plant, show strong plant growth
Inhibitory action, can control plant growth, diseases prevention effect resistant to lodging be reached, while having bactericidal action concurrently.The mid-1970s, it is first
The appearance of triazole bactericidal agent triazolone, has started the new classification of bactericide.Because its a variety of pathogen to crop has height
Effect, interior suction, broad-spectrum action, and as having a wide range of application at present, application method is flexible, prevention effect good, most development and application are latent
One class efficient germicide of power.But its unreasonable uses can cause potential health threat and pollution of ecological environment to the mankind, its
Residue problem in food is received more and more attention.
Because triazole pesticide residual quantity is low in tealeaves, extracts and generally carried out using traditional liquid-liquid extraction or spe pillars
Need to use multi-solvents in extraction, whole process, complex operation step causes a large amount of losses of composition to be measured, extraction efficiency
It is not high, it have impact on final accuracy of detection and accuracy.
The content of the invention
For above-mentioned technical problem of the prior art, the invention provides in a kind of analysis tealeaves efficiently, easy three
The method of azoles farm chemicals residual quantity.
To achieve these goals, the technical scheme that provides of the present invention is：Side for determining Pesticide Residues in Tea amount
Method, this method comprises the following steps：
(1) sample pre-treatments：After tealeaves is crushed, after being dissolved with water, with acetonitrile-acetone solution ultrasonic extraction, after centrifugation
Obtain extract；
(2) stirring rod SPE：The stirring rod of polymer-graphite ene coatings is coated with to immerse into above-mentioned extract
Carry out SPE；
(3) gas chromatography-mass spectrum is detected,
Wherein, residues of pesticides remain for triazole pesticide；Polymer-graphite ene coatings in stirring rod are specially that shell gathers
Sugar-graphite ene coatings.
Further, triazole pesticide residual be paclobutrazol, triapenthenol, hexaconazole, uniconazole P, nitrile bacterium azoles, Flusilazole,
Propiconazole, triazolone, Tebuconazole, bromuconazole, Difenoconazole, olefin conversion, simeconazoles and Bian chlorine Triadimenol.
Further, the step (1) is specially：Take after the crushing of 1-2g tealeaves, use 80-100ml deionized water dissolvings, use 5-
10ml volume ratios carry out ultrasonic extraction for 2: 3 acetonitrile-acetone solution, and ultrasonic time is 10-15min, then carry out centrifugation 5-
10min, centrifugal rotational speed is controlled in 8000-10000r/mmin, obtains extract.
Further, the step (2) is specially：The stirring rod for being coated with polymer-graphite ene coatings is immersed to above-mentioned
In extract, 15-25min is stirred by magnetic agitation mode in the environment of closing, SPE is carried out.
Further, the step (3) is specially：This method selects DB-5MS, 30m × 0.25mm × 0.25 μm, quartz wool
Capillary column, chromatogram column and programmed temperature is：50 DEG C, 1min is kept, 120 DEG C are risen to 15 DEG C/min, 1min is kept, with 10 DEG C/min
180 DEG C are risen to, 2min is kept, 280 DEG C are risen to 5 DEG C/min, 2min is kept, 320 DEG C are risen to 20 DEG C/min, 10min is kept；
Carrier gas is high pure nitrogen, flow velocity 1.5mL/min, electron bombardment ionization source EI, 300 DEG C of injector temperature, chromatography-mass spectroscopy interface temperature
280 DEG C, 250 DEG C of ion source temperature, ionizing energy：70eV, using Splitless injecting samples, sample size：1 μ L, solvent delay：5min,
Select leaving office Mode S IM.
By the above method, the present invention possesses following advantage：
1st, the stirring rod with chitosan-graphite ene coatings is incorporated into triazole pesticide residual field first, due to shell
The excellent dispersive property of glycan-graphene and purification extracted character, while greatly simplifying conventional solid extraction elution process, pole
Sample loss is reduced greatly, extraction efficiency and accuracy of detection is improved.Further, the selection characteristic based on triazole pesticide,
Found by lot of experiments, by Optimized Extraction parameter, use the stirring rod of the graphite ene coatings with chitosan-modification can be with
Fast and effeciently triazole pesticide in tealeaves is fully extracted, a variety of triazole pesticide residuals are realized while the skill of detection
Art effect.
2nd, the triazole pesticide in tealeaves is carried out just to carry for 2: 3 acetonitrile-acetone using volume ratio, can effectively will be non-agricultural
Medicine residuals are separated, and by being contrasted with traditional single extractant acetone, acetonitrile, ethyl acetate, the application is adopted
Acetonitrile-acetone mixed liquor extraction efficiency is high, and the removal ability of impurity component is strong, can in tealeaves is retained most of triazole
While pesticide residue, the content of the interference components such as organophosphor, organophosphor is reduced as far as possible.
3rd, during gas-chromatography, optimize by lot of experiments, for what is obtained under specific extraction conditions in the application
Solution to be measured, by using the Temperature Programmed Processes in the application can realize 14 kinds of triazole matters efficiently separate with it is qualitative
Quantitative detection, during inner mark method ration, the detection limit of triazole pesticide reaches 9 μ g/kg in 14, and relative standard is partially
1.9-6.8%, the range of linearity is 0.010-0.5mg/kg.
Embodiment
Triazole pesticide residual quantity in tealeaves is detected using gas chromatography combined with mass spectrometry technology for further explaination,
It is described in more detail with reference to example.
1st, test portion
(1) sample pre-treatments：Take after the crushing of 2g tealeaves, use 100ml deionized water dissolvings, with the second that 6ml volume ratios are 2: 3
Nitrile-acetone soln carries out ultrasonic extraction, and ultrasonic time is 15min, then carries out centrifugation 8min, and centrifugal rotational speed control exists
10000r/mmin, obtains extract.
(2) stirring rod SPE：The stirring rod for being coated with chitosan-graphite ene coatings is immersed to above-mentioned extract
In, 20min is stirred by magnetic agitation mode in the environment of closing, SPE is carried out.
Wherein, the preparation method of chitosan-graphite ene coatings is：By esterification, graphene is entered using chitosan
Row surface is modified to be obtained, and the chitin modified grapheme material prepared grafts to stirring rod table by in-situ polymerization mode
Face, and nano-scale chitosan-graphite ene coatings are formed in stirring rod, the stirring rod prepared is stored in acetonitrile solvent, standby
With.
(3) after stirring rod is volatilized in nitrogen, with extraction of substance in 1ml acetonitriles immersion dissolving stirring rod, then carry out, gas
Phase chromatography-mass spectroscopy is detected.Wherein, gas chromatography-mass spectrum testing conditions are：The μ of chromatographic column DB-5MS, 30m × 0.25mm × 0.25
M, quartz capillary column, chromatogram column and programmed temperature is：50 DEG C, 1min is kept, 120 DEG C are risen to 15 DEG C/min, 1min is kept, with
10 DEG C/min rises to 180 DEG C, keeps 2min, and 280 DEG C are risen to 5 DEG C/min, keeps 2min, and 320 DEG C, guarantor are risen to 20 DEG C/min
Hold 10min；Carrier gas is high pure nitrogen, flow velocity 1.5mL/min, electron bombardment ionization source EI, 300 DEG C of injector temperature, and chromatography-mass spectroscopy connects
280 DEG C of temperature of mouth, 250 DEG C of ion source temperature, ionizing energy：70eV, using Splitless injecting samples, sample size：1 μ L, solvent delay：
5min, selection leaving office Mode S IM.
2nd, testing result
Testing result is shown in Table 1：
| Numbering | Pesticide variety | Retention time/min | Qualitative ion |
| 1 | Paclobutrazol | 7.18 | 236 |
| 2 | Triapenthenol | 7.98 | 206 |
| 3 | Hexaconazole | 9.80 | 214 |
| 4 | Uniconazole P | 10.53 | 236 |
| 5 | Nitrile bacterium azoles | 13.95 | 179 |
| 6 | Flusilazole | 16.59 | 233 |
| 7 | Propiconazole | 19.08 | 259 |
| 8 | Triazolone | 19.94 | 208 |
| 9 | Tebuconazole | 22.23 | 250 |
| 10 | Bromuconazole | 23.12 | 173 |
| 11 | Difenoconazole | 25.13 | 323 |
| 12 | Olefin conversion | 28.52 | 268 |
| 13 | Simeconazoles | 30.25 | 276 |
| 14 | Bian chlorine Triadimenol | 32.01 | 292 |
Finally it should be noted that：The preferred embodiments of the present invention are the foregoing is only, are not intended to limit the invention,
Although the present invention is described in detail with reference to the foregoing embodiments, for those skilled in the art, it still may be used
To be modified to the technical scheme described in foregoing embodiments, or equivalent substitution is carried out to which part technical characteristic.
Within the spirit and principles of the invention, any modification, equivalent substitution and improvements made etc., should be included in the present invention's
Within protection domain.
Claims (6)
1. a kind of method for determining Pesticide Residues in Tea amount, it is characterised in that this method comprises the following steps：
(1) sample pre-treatments：After tealeaves is crushed, after being dissolved with water, with acetonitrile-acetone solution ultrasonic extraction, obtained after centrifugation
Extract；
(2) stirring rod SPE：It is coated with the stirring rod of polymer-graphite ene coatings and immerses into above-mentioned extract progress
SPE；
(3) gas chromatography-mass spectrum is detected,
Wherein, residues of pesticides remain for triazole pesticide；Polymer-graphite ene coatings in stirring rod are specially chitosan-stone
Black ene coatings.
2. according to the method described in claim 1, it is characterised in that the triazole pesticide residual is paclobutrazol, triapenthenol, oneself
Azoles alcohol, uniconazole P, nitrile bacterium azoles, Flusilazole, propiconazole, triazolone, Tebuconazole, bromuconazole, Difenoconazole, olefin conversion, fluosilicic
Azoles and Bian chlorine Triadimenol.
3. according to the method described in claim 1, it is characterised in that step (1) is specially：Take after the crushing of 1-2g tealeaves, use 80-
100ml deionized water dissolvings, carry out ultrasonic extraction, ultrasonic time is with 5-10ml volume ratios for 2: 3 acetonitrile-acetone solution
10-15min, then carries out centrifugation 5-10min, and centrifugal rotational speed is controlled in 8000-10000r/min, obtains extract.
4. according to the method described in claim 1, it is characterised in that step (2) is specially：It is coated with polymer-graphite alkene
The stirring rod of coating is immersed into above-mentioned extract, is stirred 15-25min by magnetic agitation mode in the environment of closing, is entered
Row SPE.
5. according to the method described in claim 1, it is characterised in that the preparation method of the chitosan-graphite ene coatings is：It is logical
Over-churning reacts, and carries out that surface is modified obtains to graphene using chitosan, the chitin modified graphene material prepared
Material grafts to stirring rod surface by in-situ polymerization mode, and forms nano-scale chitosan-graphite ene coatings in stirring rod, makes
The stirring rod got ready is stored in acetonitrile solvent, standby.
6. according to the method described in claim 1, it is characterised in that step (3) is specially：This method selects DB-5MS, and 30m ×
0.25mm × 0.25 μm, quartz capillary column, chromatogram column and programmed temperature is：50 DEG C, 1min is kept, 120 are risen to 15 DEG C/min
DEG C, keep 1min, 180 DEG C risen to 10 DEG C/min, keep 2min, 280 DEG C are risen to 5 DEG C/min, keep 2min, with 20 DEG C/
Min rises to 320 DEG C, keeps 10min；Carrier gas is high pure nitrogen, flow velocity 1.5mL/min, electron bombardment ionization source EI, injector temperature
300 DEG C, 280 DEG C of chromatography-mass spectroscopy interface temperature, 250 DEG C of ion source temperature, ionizing energy：70eV, using Splitless injecting samples, enters
Sample amount：1 μ L, solvent delay：5min, choice ion pattern SIM.
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Inventor after: Sun Tunan Inventor after: Han Wenjun Inventor before: Yuan Xiaolin |
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Effective date of registration: 20170629 Address after: 266021 Shandong province Qingdao City, Hangzhou Road No. 16 Applicant after: Sun Tunan Address before: 523000 Dongcheng District City, Dongguan province old cattle Wai Wai Village Industrial Zone Applicant before: Yuan Xiaolin |
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Effective date of registration: 20190301 Address after: 257 300 Dongying Agricultural High-tech Industrial Demonstration Zone, Shandong Province Patentee after: Shandong Yuanzheng Testing Technology Co., Ltd. Address before: 266021 No. 16 Hangzhou Road, North District, Qingdao City, Shandong Province Patentee before: Sun Tunan |