CN105277640B - 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
- Publication number
- CN105277640B CN105277640B CN201510822993.5A CN201510822993A CN105277640B CN 105277640 B CN105277640 B CN 105277640B CN 201510822993 A CN201510822993 A CN 201510822993A CN 105277640 B CN105277640 B CN 105277640B
- Authority
- CN
- China
- Prior art keywords
- stirring rod
- ene coatings
- graphite ene
- specially
- spe
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 238000000034 method Methods 0.000 title claims abstract description 24
- 239000000447 pesticide residue Substances 0.000 title claims abstract description 8
- 238000003756 stirring Methods 0.000 claims abstract description 23
- 238000000576 coating method Methods 0.000 claims abstract description 18
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 16
- 239000010439 graphite Substances 0.000 claims abstract description 16
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims abstract description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000001514 detection method Methods 0.000 claims abstract description 9
- 238000004949 mass spectrometry Methods 0.000 claims abstract description 6
- 238000002137 ultrasound extraction Methods 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000005119 centrifugation Methods 0.000 claims abstract description 5
- 239000000575 pesticide Substances 0.000 claims abstract description 4
- 238000002203 pretreatment Methods 0.000 claims abstract description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 7
- RGEDHOUMJZSPRH-UHFFFAOYSA-N acetonitrile;methanol;propan-2-one Chemical compound OC.CC#N.CC(C)=O RGEDHOUMJZSPRH-UHFFFAOYSA-N 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- 229910021389 graphene Inorganic materials 0.000 claims description 5
- -1 Caojinjing Chemical compound 0.000 claims description 4
- 238000001819 mass spectrum Methods 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- GDNFGRAJXOKRJW-UHFFFAOYSA-N 6-chloro-4-n-cyclopropyl-2-n-propan-2-yl-1,3,5-triazine-2,4-diamine;s-ethyl n,n-diethylcarbamothioate Chemical compound CCSC(=O)N(CC)CC.CC(C)NC1=NC(Cl)=NC(NC2CC2)=N1 GDNFGRAJXOKRJW-UHFFFAOYSA-N 0.000 claims description 3
- 229920002101 Chitin Polymers 0.000 claims description 3
- 238000013019 agitation Methods 0.000 claims description 3
- RQVYBGPQFYCBGX-UHFFFAOYSA-N ametryn Chemical compound CCNC1=NC(NC(C)C)=NC(SC)=N1 RQVYBGPQFYCBGX-UHFFFAOYSA-N 0.000 claims description 3
- 239000012159 carrier gas Substances 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- AAEVYOVXGOFMJO-UHFFFAOYSA-N prometryn Chemical compound CSC1=NC(NC(C)C)=NC(NC(C)C)=N1 AAEVYOVXGOFMJO-UHFFFAOYSA-N 0.000 claims description 3
- LFULEKSKNZEWOE-UHFFFAOYSA-N propanil Chemical compound CCC(=O)NC1=CC=C(Cl)C(Cl)=C1 LFULEKSKNZEWOE-UHFFFAOYSA-N 0.000 claims description 3
- WJNRPILHGGKWCK-UHFFFAOYSA-N propazine Chemical compound CC(C)NC1=NC(Cl)=NC(NC(C)C)=N1 WJNRPILHGGKWCK-UHFFFAOYSA-N 0.000 claims description 3
- ODCWYMIRDDJXKW-UHFFFAOYSA-N simazine Chemical compound CCNC1=NC(Cl)=NC(NCC)=N1 ODCWYMIRDDJXKW-UHFFFAOYSA-N 0.000 claims description 3
- MGLWZSOBALDPEK-UHFFFAOYSA-N simetryn Chemical compound CCNC1=NC(NCC)=NC(SC)=N1 MGLWZSOBALDPEK-UHFFFAOYSA-N 0.000 claims description 3
- IROINLKCQGIITA-UHFFFAOYSA-N terbutryn Chemical compound CCNC1=NC(NC(C)(C)C)=NC(SC)=N1 IROINLKCQGIITA-UHFFFAOYSA-N 0.000 claims description 3
- 239000005583 Metribuzin Substances 0.000 claims description 2
- 238000011065 in-situ storage Methods 0.000 claims description 2
- FOXFZRUHNHCZPX-UHFFFAOYSA-N metribuzin Chemical compound CSC1=NN=C(C(C)(C)C)C(=O)N1N FOXFZRUHNHCZPX-UHFFFAOYSA-N 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 239000010453 quartz Substances 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims 1
- 239000004575 stone Substances 0.000 claims 1
- 238000002604 ultrasonography Methods 0.000 claims 1
- 229920000642 polymer Polymers 0.000 abstract 2
- NIQQIJXGUZVEBB-UHFFFAOYSA-N methanol;propan-2-one Chemical compound OC.CC(C)=O NIQQIJXGUZVEBB-UHFFFAOYSA-N 0.000 abstract 1
- 238000000605 extraction Methods 0.000 description 9
- 230000000694 effects Effects 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000003905 agrochemical Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- MXWJVTOOROXGIU-UHFFFAOYSA-N atrazine Chemical compound CCNC1=NC(Cl)=NC(NC(C)C)=N1 MXWJVTOOROXGIU-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N methyl alcohol Substances OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 244000025254 Cannabis sativa Species 0.000 description 1
- 239000012494 Quartz wool Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 230000002070 germicidal effect Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000000622 liquid--liquid extraction Methods 0.000 description 1
- 239000006249 magnetic particle Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 230000008635 plant growth Effects 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
Landscapes
- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
- Sampling And Sample Adjustment (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
A kind of method for determining Pesticide Residues in Tea amount, comprises the following steps：(1) sample pre-treatments：After tealeaves is crushed, with water dissolves after, with acetonitrile and acetone methanol 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 detection, wherein, residues of pesticides are remained for triazine；Polymer graphite ene coatings in stirring rod are specially shitosan graphite ene coatings.The application can realize being detected efficiently, easily to Pesticide Residues in Tea amount.
Description
Technical field
Gas chromatography-mass spectrum is utilized to triazine 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
Triazine is organic heterocyclic class compound, has the effect of sterilized and coordinate plant growth concurrently, is answered as current
With scope it is wide, application method is flexible, prevention effect good, a class efficient germicide of most development and application potentiality.But its is unreasonable
Using can the mankind be caused with potential health threat and pollution of ecological environment, its residue problem in food is subject to more and more
Concern.
Because triazine residual quantity is low in tealeaves, extraction is generally carried out using traditional liquid-liquid extraction or spe pillars
Extraction, needs to use multi-solvents in whole process, and complex operation step causes a large amount of losses of composition to be measured, extraction efficiency
It is not high, have impact on final accuracy of detection and accuracy.
At present, although have researcher that Graphene is incorporated into the detection process of triazines residue, but use magnetic
Property graphene nano particle is extracted, on the one hand, nano-particle bad dispersibility, the effect of extracting of agricultural chemicals is undesirable, another side
Operating procedure is complicated, and follow-up cleaning treatment process is difficult, and the magnetic particle rate of recovery is low, causes testing cost higher, it is impossible to extensively
Using.
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 piperazine pesticide residue amount.
To achieve these goals, the technical scheme of present invention offer is：Side for determining Pesticide Residues in Tea amount
Method, the method comprises the following steps：
(1) sample pre-treatments：After tealeaves is crushed, with water dissolves after, with acetonitrile-acetone-methanol solution ultrasonic extraction, from
Extract is obtained after the heart；
(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 detection,
Wherein, residues of pesticides are triazine residual；Polymer-graphite ene coatings in stirring rod are specially shell and gather
Sugar-graphite ene coatings.
Further, the triazine residual is propazine, Zhong Dingtong, Atrazine, Garagard, Simanex, piperazine grass
Ketone, Prefox, Caojinjing, prometryn, ametryn, terbutryn, symetryne, propanil.
Further, the step (1) is specially：After taking the crushing of 1-2g tealeaves, 80-100ml deionized water dissolvings are used, use 5-
10ml volume ratios carry out ultrasonic extraction for 2: 3: 1 acetonitrile-acetone-methanol solution, and ultrasonic time is 20-25min, is then carried 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, carry out SPE.
Further, the step (3) is specially：This method selects HP-5MS, 30m × 0.25mm × 0.25 μm, quartz wool
Capillary column, chromatogram column and programmed temperature is：70 DEG C, 1min is kept, 150 DEG C are risen to 15 DEG C/min, 2min is kept, with 10 DEG C/min
220 DEG C are risen to, 3min is kept, 280 DEG C are risen to 5 DEG C/min, keep 1min, 320 DEG C are risen to 25 DEG C/min, keep 10min；
Carrier gas is high pure nitrogen, flow velocity 1.5mL/min, electron bombardment ionization source EI, 310 DEG C of injector temperature, chromatography-mass spectroscopy interface temperature
290 DEG C, 260 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.
By the above method, the present invention possesses following advantage：
1st, the stirring rod with shitosan-graphite ene coatings is incorporated into triazine 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 improve.Further, the selection characteristic based on triazine,
Found by lot of experiments, by Optimized Extraction parameter, use the stirring rod with chitin modified graphite ene coatings can be with
Fast and effeciently triazine in tealeaves is fully extracted, the skill of various triazine residual detections simultaneously is realized
Art effect.
2nd, can have for 2: 3: 1 acetonitrile-acetone-methyl alcohol carries out just carrying to the triazine in tealeaves using volume ratio
Effect separates non-agricultural chemicals residuals, is carried out by with traditional single extractant acetone, acetonitrile, ethyl acetate equal solvent
Contrast, acetonitrile-acetone-methyl alcohol mixed liquor extraction efficiency that the application is used is high, and the removal ability of impurity component is strong, can protect
While staying that most of triazine is remained in tealeaves, 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 13 kinds of triazines materials efficiently separate with it is qualitative
Quantitative determination, by inner mark method ration during, the detection limit of triazine reaches 9 μ g/kg in 13, and relative standard is partially
1.3-6.8%, the range of linearity is 0.010-0.5mg/kg.
Specific embodiment
For further explaination is detected using gas chromatography combined with mass spectrometry technology to triazine residual quantity in tealeaves,
It is described in more detail with reference to example.
1st, test portion
(1) sample pre-treatments：After taking the crushing of 2g tealeaves, 100ml deionized water dissolvings are used, be 2: 3: 1 with 6ml volume ratios
Acetonitrile-acetone-methanol solution carries out ultrasonic extraction, and ultrasonic time is 15min, then carries out centrifugation 8min, centrifugal rotational speed control
In 10000r/mmin, extract is obtained.
(2) stirring rod SPE：The stirring rod for being coated with shitosan-graphite ene coatings is immersed to above-mentioned extract
In, 25min is stirred by magnetic agitation mode in the environment of closing, carry out SPE.
Wherein, the preparation method of shitosan-graphite ene coatings is：By esterification, Graphene is entered using shitosan
Row surface is modified to be obtained, and the chitin modified grapheme material for preparing 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 for preparing is stored in acetonitrile solvent, standby
With.
(3) after stirring rod is volatilized in nitrogen, extraction of substance in dissolving stirring rod is soaked with 1ml acetonitriles, is then carried out, gas
Phase chromatography-mass spectroscopy is detected.Wherein, gas chromatography-mass spectrum testing conditions are：Chromatographic column HP-5MS, 30m × 0.25mm × 0.25 μ
M, quartz capillary column, chromatogram column and programmed temperature is：70 DEG C, 1min is kept, 150 DEG C are risen to 15 DEG C/min, keep 2min, with
10 DEG C/min rises to 220 DEG C, keeps 3min, and 280 DEG C are risen to 5 DEG C/min, keeps 1min, and 320 DEG C are risen to 25 DEG C/min, protects
Hold 10min；Carrier gas is high pure nitrogen, flow velocity 1.5mL/min, electron bombardment ionization source EI, 310 DEG C of injector temperature, and chromatography-mass spectroscopy connects
290 DEG C of temperature of mouth, 260 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 | Propazine | 6.89 | 214 |
| 2 | Zhong Dingtong | 8.12 | 226 |
| 3 | Atrazine | 9.32 | 200 |
| 4 | Garagard | 14.65 | 214 |
| 5 | Terbutryn | 15.24 | 185 |
| 6 | Metribuzin | 17.86 | 215 |
| 7 | Prefox | 18.67 | 212 |
| 8 | Caojinjing | 19.98 | 241 |
| 9 | Prometryn | 22.73 | 241 |
| 10 | Ametryn | 24.10 | 227 |
| 11 | Simanex | 26.34 | 202 |
| 12 | Symetryne | 27.19 | 213 |
| 13 | Propanil | 30.07 | 218 |
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 being described in detail to the present invention with reference to the foregoing embodiments, for a person skilled in the art, it still may be used
Modified with to the technical scheme described in foregoing embodiments, or equivalent is carried out to which part technical characteristic.
All any modification, equivalent substitution and improvements within the spirit and principles in the present invention, made etc., should be included in of the invention
Within protection domain.
Claims (6)
1. a kind of method for determining Pesticide Residues in Tea amount, it is characterised in that the method comprises the following steps：
(1) sample pre-treatments：After tealeaves is crushed, with water dissolves after, with acetonitrile-acetone-methanol solution ultrasonic extraction, after centrifugation
Obtain extract；
(2) stirring rod SPE：It is coated with the stirring rod of polymer-graphite ene coatings and immerses to be carried out into above-mentioned extract
SPE；
(3) gas chromatography-mass spectrum detection,
Wherein, residues of pesticides are triazine residual；Polymer-graphite ene coatings in stirring rod are specially shitosan-stone
Black ene coatings.
2. method according to claim 1, it is characterised in that the triazine residual is propazine, Zhong Dingtong, Ah
Te Lajin, Garagard, Simanex, metribuzin, Prefox, Caojinjing, prometryn, ametryn, terbutryn, symetryne, propanil.
3. method according to claim 1, it is characterised in that step (1) is specially：After taking the crushing of 1-2g tealeaves, 80- is used
100ml deionized water dissolvings, with 5-10ml volume ratios for 2: 3: 1 acetonitrile-acetone-methanol solution carries out ultrasonic extraction, ultrasound
Time is 20-25min, then carries out centrifugation 5-10min, and centrifugal rotational speed is controlled in 8000-10000r/min, obtains extract.
4. method according to 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, and 15-25min is stirred by magnetic agitation mode in the environment of closing, is entered
Row SPE.
5. method according to claim 1, it is characterised in that the preparation method of the shitosan-graphite ene coatings is：It is logical
Over-churning reacts, and carries out the chitin modified Graphene material that surface is modified to be obtained, and is prepared to Graphene using shitosan
Material grafts to stirring rod surface by in-situ polymerization mode, and nano-scale chitosan-graphite ene coatings, system are formed in stirring rod
The stirring rod got ready is stored in acetonitrile solvent, standby.
6. method according to claim 1, it is characterised in that step (3) is specially：This method selects HP-5MS, and 30m ×
0.25mm × 0.25 μm, quartz capillary column, chromatogram column and programmed temperature is：70 DEG C, 1min is kept, 150 are risen to 15 DEG C/min
DEG C, keep 2min, rise to 220 DEG C with 10 DEG C/min, keep 3min, rise to 280 DEG C with 5 DEG C/min, keep 1min, with 25 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
310 DEG C, 290 DEG C of chromatography-mass spectroscopy interface temperature, 260 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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510822993.5A CN105277640B (en) | 2015-11-23 | 2015-11-23 | A kind of method for determining Pesticide Residues in Tea amount |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510822993.5A CN105277640B (en) | 2015-11-23 | 2015-11-23 | A kind of method for determining Pesticide Residues in Tea amount |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105277640A CN105277640A (en) | 2016-01-27 |
| CN105277640B true CN105277640B (en) | 2017-06-16 |
Family
ID=55147010
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510822993.5A Active CN105277640B (en) | 2015-11-23 | 2015-11-23 | A kind of method for determining Pesticide Residues in Tea amount |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105277640B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108181393B (en) * | 2017-12-25 | 2021-01-22 | 广州广电计量检测股份有限公司 | Method for detecting hydroxyethyl hexahydro-s-triazine in plastic product |
| CN109270228A (en) * | 2018-11-24 | 2019-01-25 | 广西中医药大学附属瑞康医院 | A kind of Monitoring Pesticide Residues method and system based on graphene sensor |
| CN109946401A (en) * | 2019-04-08 | 2019-06-28 | 西南林业大学 | A method of metribuzin pesticide residue is detected with gas-chromatography-nitrogen chemical luminescence detector |
| CN112697916A (en) * | 2020-12-18 | 2021-04-23 | 华南理工大学 | Method for detecting triazine pesticide in soil |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102914608B (en) * | 2012-11-12 | 2013-10-30 | 天津出入境检验检疫局动植物与食品检测中心 | Method for quickly detecting pesticide multiple residues in traditional Chinese medicine through membrane separation and comprehensive two-dimensional gas chromatography-time-of-flight mass spectrometer |
| SG11201506641RA (en) * | 2013-03-15 | 2015-09-29 | Univ Nanyang Tech | Hybrid nanomaterial of graphene oxide nanomaterial and cationic quaternized chitosan |
| CN104974371B (en) * | 2014-04-11 | 2018-06-15 | 山东大学 | A kind of preparation method of graphene-chitosan multi-porous composite material |
-
2015
- 2015-11-23 CN CN201510822993.5A patent/CN105277640B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN105277640A (en) | 2016-01-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105277640B (en) | A kind of method for determining Pesticide Residues in Tea amount | |
| Yang et al. | Use of magnetic effervescent tablet-assisted ionic liquid dispersive liquid–liquid microextraction to extract fungicides from environmental waters with the aid of experimental design methodology | |
| Santos et al. | Evaluation of microwave and ultrasound extraction procedures for arsenic speciation in bivalve mollusks by liquid chromatography–inductively coupled plasma-mass spectrometry | |
| Aggarwal et al. | A review on the determination of isotope ratios of boron with mass spectrometry | |
| Talebi et al. | Optimization of the extraction of paclitaxel from Taxus baccata L. by the use of microwave energy | |
| Hou et al. | The use of silica‐coated magnetic graphene microspheres as the adsorbent for the extraction of pyrethroid pesticides from orange and lettuce samples followed by GC–MS analysis | |
| Lu et al. | Simultaneous determination of pyrethrins residues in teas by ultra-performance liquid chromatography/tandem mass spectrometry | |
| Beauchemin | Environmental analysis by inductively coupled plasma mass spectrometry | |
| CN102735784A (en) | Method for simultaneously determining one hundred pesticide residuals in traditional Chinese medicine through ultrahigh performance liquid chromatography-tandem quadrupole mass spectrum | |
| Grinberg et al. | Ultra-trace determination of iodine in sediments and biological material using UV photochemical generation-inductively coupled plasma mass spectrometry | |
| Vallecillos et al. | Determination of musk fragrances in sewage sludge by pressurized liquid extraction coupled to automated ionic liquid‐based headspace single‐drop microextraction followed by GC‐MS/MS | |
| CN112198258B (en) | Method for synchronously extracting and analyzing polybrominated diphenyl ethers, hydroxyl polybrominated diphenyl ethers and methoxy polybrominated diphenyl ethers in plants | |
| Fumes et al. | Determination of pesticides in sugarcane juice employing microextraction by packed sorbent followed by gas chromatography and mass spectrometry | |
| Prestes et al. | Comparison of several extraction procedures for the determination of biopesticides in soil samples by ultrahigh pressure LC‐MS/MS | |
| Zhao et al. | Rapid determination of organonitrogen, organophosphorus and carbamate pesticides in tea by ultrahigh-performance liquid chromatography–tandem mass spectrometry (UPLC-MS/MS) | |
| Fang et al. | An ionic liquid improved HPLC-ICP-MS method for simultaneous determination of arsenic and selenium species in animal/plant-derived foodstuffs | |
| CN105241981B (en) | A kind of method for determining Pesticide Residues in Tea amount | |
| Gil‐García et al. | Simple, rapid solid‐phase extraction procedure for the determination of ultra‐trace levels of pyrethroids in ground and sea water by liquid chromatography/electrospray ionization mass spectroscopy | |
| Liang et al. | Determination of four sulfonylurea herbicides in tea by matrix solid‐phase dispersion cleanup followed by dispersive liquid–liquid microextraction | |
| CN112858542B (en) | Liquid chromatography mass spectrometry method for measuring atrazine, imidacloprid and metabolites thereof in leaves | |
| CN111380980A (en) | Method for detecting pesticide residue on fruits and vegetables | |
| Amaral et al. | Evaluation of sample preparation procedures and krypton as an interference standard probe for arsenic speciation by HPLC-ICP-QMS | |
| CN105277645B (en) | A kind of method for determining Pesticide Residues in Tea amount | |
| Wang et al. | Determination of multiclass pesticide residues in apple juice by gas chromatography–mass spectrometry with large‐volume injection | |
| JP2006078419A (en) | Analytical method and analytical system for pesticide |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB03 | Change of inventor or designer information |
Inventor after: Chang Qing Inventor after: Wang Guojun Inventor before: Yuan Xiaolin |
|
| CB03 | Change of inventor or designer information | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20170515 Address after: 710077, Xi'an hi tech Zone, Kam Yip Road, 69, pioneering research and Development Park, C District 6, 1, 1, nine, 10101, room, floor, Shaanxi Applicant after: XI'AN CCQT CO., LTD. Address before: 523000 Dongcheng District City, Dongguan province old cattle Wai Wai Village Industrial Zone Applicant before: Yuan Xiaolin |
|
| TA01 | Transfer of patent application right | ||
| GR01 | Patent grant | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: Method for measuring pesticide residue amount in tea leaves Effective date of registration: 20180823 Granted publication date: 20170616 Pledgee: Xi'an innovation financing Company limited by guarantee Pledgor: XI'AN CCQT CO., LTD. Registration number: 2018990000736 |
|
| PE01 | Entry into force of the registration of the contract for pledge of patent right | ||
| PC01 | Cancellation of the registration of the contract for pledge of patent right |
Date of cancellation: 20181211 Granted publication date: 20170616 Pledgee: Xi'an innovation financing Company limited by guarantee Pledgor: XI'AN CCQT CO., LTD. Registration number: 2018990000736 |
|
| PC01 | Cancellation of the registration of the contract for pledge of patent right | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: Method for measuring pesticide residue amount in tea leaves Effective date of registration: 20181217 Granted publication date: 20170616 Pledgee: Xi'an innovation financing Company limited by guarantee Pledgor: XI'AN CCQT CO., LTD. Registration number: 2018610000232 |
|
| PE01 | Entry into force of the registration of the contract for pledge of patent right | ||
| PC01 | Cancellation of the registration of the contract for pledge of patent right | ||
| PC01 | Cancellation of the registration of the contract for pledge of patent right |
Date of cancellation: 20210209 Granted publication date: 20170616 Pledgee: Xi'an innovation financing Company limited by guarantee Pledgor: XI'AN CCQT Co.,Ltd. Registration number: 2018610000232 |