CN103399099A - Method for detecting nine organophosphorus pesticides simultaneously - Google Patents
Method for detecting nine organophosphorus pesticides simultaneously Download PDFInfo
- Publication number
- CN103399099A CN103399099A CN2013103523711A CN201310352371A CN103399099A CN 103399099 A CN103399099 A CN 103399099A CN 2013103523711 A CN2013103523711 A CN 2013103523711A CN 201310352371 A CN201310352371 A CN 201310352371A CN 103399099 A CN103399099 A CN 103399099A
- Authority
- CN
- China
- Prior art keywords
- molecularly imprinted
- organophosphorus pesticides
- extraction
- organophosphorus
- detecting
- 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.)
- Granted
Links
Images
Landscapes
- Sampling And Sample Adjustment (AREA)
- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
- Investigating Or Analysing Biological Materials (AREA)
Abstract
The invention relates to a method for detecting nine organophosphorus pesticides simultaneously. The method for detecting nine organophosphorus pesticides simultaneously comprises the following steps: preparing multi-recognition-site molecularly imprinted polymers, and establishing a molecularly imprinted matrix solid-phase dispersion extraction and gas chromatography combination system. Nine molecularly imprinted polymers, including dipterex, with high selection recognition performance act as adsorption functional materials, and the defects of sole recognition of traditional molecularly imprinted polymers and the like are prevented; the molecularly imprinted matrix solid-phase dispersion extraction and the gas chromatography are combined, and then the rapid and flexible detection method with a wide detection range to nine trace organophosphorus pesticides including dipterex is established. The method for detecting nine organophosphorus pesticides simultaneously provided by the invention is low in cost, simple in experiment operation and high in flexibility, and is suitable for the rapid detection on nine trace organophosphorus pesticides including dipterex in various products.
Description
Technical field
The present invention relates to a kind of method that detects simultaneously Determination of Organophosphorus Pesticide, belong to the food safety detection technical field.
Background technology
Organophosphorus pesticide, because of unstable chemcial property, easily decomposes, and the half life period is short, is difficult at crop, animal and human's body accumulation, thereby is used widely.But because the organophosphorus usable range is more and more wider, frequency of utilization is more and more higher, and amount of application is increasing, has become the most serious agricultural chemicals of contaminated food products [1].A large amount of organophosphorus pesticides exceed standard and not only pollute agricultural product and ecologic environment, also will jeopardize health and life security.The agricultural product that long-term edible organophosphorus pesticide trace exceeds standard, may cause people's slow poisoning, causes the generation of disease, and even impact is of future generation.Edible serious vegetables or the fruit of organophosphorus pesticide, the lighter there will be the symptoms such as headache, dizziness, nauseating, stomachache, and severe one can cause expiratory dyspnea, spasm, stupor, and more severe patient even can threaten people's life security.As acetylcholine inhibitor, the environmental exposure of organophosphorus pesticide and skin contact also can cause biotoxication.
It is the focus of International Food Safety Control area research and development that pesticide multi-residues detects, at present the main methods such as gas chromatography, liquid chromatography, immunoassay, gas chromatography-mass spectrum (GC-MS) and liquid chromatography-mass spectrography (LC-MS) that adopt.The chromatography mass spectrometry detection sensitivity is high but expensive.Chromatography detects limit for height and (is generally 10-500 μ g kg
-1), (Japanese positive list is 10 μ g kg to the Pesticide Residue value can not to meet the actual needs that trace residues of pesticides and the export trade detect
-1), therefore usually need to carry out enrichment before analyzing.The pre-treating method that adopts at present mainly contains Solid-Phase Extraction, liquid-liquid extraction, Dispersive solid phase extraction, solid-phase microextraction, supercritical fluid extraction and column chromatography etc.Because the matrix solid phase dispersion extraction has the advantages such as amount of samples is few, the consumption organic solvent is few, the matrix solid phase dispersion extraction has been widely used in the analysis of environment, biology and food Chinese traditional medicine, organic contaminant and natural products.But often selectivity is poor based on commercial matrix solid phase dispersion extraction adsorbent, and the acting force between object and adsorbent is nonspecific, and the efficiency of extraction and cleaning is not high, be difficult to thoroughly remove the interference of matrix, and cost is also higher.Therefore the adsorbent that utilizes the synthetic adsorption functional material that Determination of Organophosphorus Pesticide is had the specific recognition ability of molecular imprinting to extract as matrix solid phase dispersion, and with the gas chromatography coupling, make testing process simple, fast and have high sensitivity, to guaranteeing that in China's food, effective examination and controlling supervision tool of organophosphorus pesticide is of great significance.
Summary of the invention
The object of the invention is to overcome long, the defect such as instrument is expensive, pre-treatment the is loaded down with trivial details detection time that exists in traditional On Detection of Organophosphorus Pesticide; a kind of method that detects simultaneously nine kinds of organophosphorus pesticides is provided, has specifically utilized the extraction of molecular engram matrix solid phase dispersion and gas chromatography coupling to detect simultaneously the method for nine kinds of organophosphorus pesticides (metrifonate, acephatemet, orthene, flolimat, Azodrin, Rogor, phosphamidon, parathion-methyl, malathion).
The present invention realizes by following steps:
1) preparation of many recognition sites molecularly imprinted polymer:
The 10mmoL 4-Aminobutanoicacid adds 5-20mL 2.5mol L
-1NaOH solution, ice bath stirs 30min; Then dropwise add 1-2mL o, the o-dimethyl thiophosphoryl chloride, regulate pH value to 10, and room temperature continues to stir 6h.Washing impurity is regulated pH to 2.0, then uses the ethyl acetate extraction potpourri.Revolve steaming, obtain common template 4-dimethoxy thiophosphoryl aminobutyric acid.
In acetonitrile solution, 4-dimethoxy thiophosphoryl aminobutyric acid, function monomer acrylamide, crosslinking chemical ethylene glycol dimethacrylate are mixed with the molar ratio of 1:3:8, then add azoisobutyronitrile to carry out polyreaction as initiating agent; The polymkeric substance that obtains is ground rear use methyl alcohol/glacial acetic acid (9:1, v/v) continuous extraction 8h, then use 100% methanol extraction 4h, obtain molecularly imprinted polymer after drying.
2) foundation of molecular engram matrix solid phase dispersion extraction-gas chromatography coupling system:
With being added with the sample 2-4g of nine kinds of organophosphorus pesticide standard solution and the molecularly imprinted polymer mixed grinding of 0.5-1.0g step 1) preparation, sample is scattered in molecularly imprinted polymer fully, said mixture is filled in empty solid-phase extraction column.First use 30mL normal hexane drip washing solid-phase extraction column, use again the methyl alcohol glacial acetic acid mixed solution (methyl alcohol: the wash-out of glacial acetic acid=95:5v/v) of 5mL, the wash-out liquid nitrogen blows the rear 0.2mL of using methylene chloride and redissolves and filter, and gets the filtrate air inlet chromatography analysis of 1 μ L, the Criterion curve.
3) the determining of organophosphorus pesticide content in determinand:
With testing sample repeating step 2) operation, calculated respectively the content of metrifonate in testing sample, acephatemet, orthene, flolimat, Azodrin, Rogor, phosphamidon, parathion-methyl, malathion by typical curve according to the peak area of gas chromatography.
Beneficial effect of the present invention:
1. the present invention is used the molecular engram polymeric material that Determination of Organophosphorus Pesticide is had high selectivity of preparation as adsorbent, has avoided the first-class shortcoming of traditional molecularly imprinted polymer identification form, has avoided the loaded down with trivial details pretreatment process of sample.
2. the present invention has highly sensitive detection method with molecular engram matrix solid phase dispersion abstraction technique and gas chromatography coupling foundation to nine kinds of organophosphorus pesticides such as metrifonate, acephatemets; realized simultaneously the Determination of Organophosphorus Pesticide in food being detected; greatly shorten analysis time, be applicable to the fast detecting of pesticide multi-residues.
3. the present invention is with low cost, and is highly sensitive, and experimental implementation is simple, is applicable to the fast detecting of organophosphorus pesticide trace residue in various agricultural product.
Description of drawings
Fig. 1 is for adding 0.02mg kg
-1The gas chromatogram of the blank sample of nine kinds of organophosphorus pesticides after molecular engram matrix solid phase dispersion extraction procedure.
Embodiment
Below in conjunction with embodiment, the present invention is further described; Following embodiment is illustrative, is not determinate, can not limit protection scope of the present invention with following embodiment.
The present invention has highly sensitive detection method with molecular engram solid phase extraction technology and gas chromatography coupling foundation to metrifonate and Azodrin.Its specific embodiment is:
1. the preparation of many recognition sites molecularly imprinted polymer:
Take 4-Aminobutanoicacid 10mmoL in 10mL2.5mol L
-1In NaOH solution, ice bath stirs 30min.With 1.215mL o, the o-dimethyl thiophosphoryl chloride dropwise adds in flask, stirs a moment.Then regulate pH to 10, room temperature continues to stir 6h, with the impurity in the ethyl acetate purging compound.Then regulate pH to 2.0, use the ethyl acetate extraction potpourri.Dry filter.Revolve to steam and remove ethyl acetate, obtain 4-dimethoxy thiophosphoryl aminobutyric acid.
The 4-dimethoxy thiophosphoryl aminobutyric acid of 2mmol preparation is dissolved in the 5mL acetonitrile solution, adds 6mmol function monomer acrylamide, 30min vibrates in oscillator.Then add 16mmol crosslinking chemical ethylene glycol dimethacrylate and 100mg initiating agent azoisobutyronitrile, fully mix rear ultrasonic 15min, logical N
215min.The round-bottomed flask of good seal is put into 58 ℃ of constant temperature water bath water-bath 24h.After the polymkeric substance that obtains was ground 200 mesh sieves with mortar, the polymkeric substance that obtains is ground rear use 200mL methyl alcohol/glacial acetic acid (4:1, v/v) continuous extraction 8h, then use 200mL100% methanol extraction 4h, 60 ℃ of vacuum drying 24h, obtain molecularly imprinted polymer.
2. the foundation of molecular engram solid phase extraction and gas chromatography coupling system
The molecularly imprinted polymer of the step 1) of using preparation, as the adsorbent of matrix solid phase dispersion extraction,, with the gas chromatography coupling, is set up the extraction of molecular engram matrix solid phase dispersion and gas chromatography coupling detection system.
A. the drafting of typical curve
Preparation variable concentrations 0.1,0.25,0.5,1.5,2.5,5.0 and 10.0mg L
-1Be added with nine kinds of organophosphorus pesticide standard solution samples such as metrifonate, respectively nine kinds of organophosphorus pesticide standard solution samples of the 2g of variable concentrations and 0.5g molecularly imprinted polymer are placed in the glass mortar mixed grinding and make sample be scattered in imprinted polymer fully, potpourri is filled in empty solid-phase extraction column.Then use 30mL normal hexane drip washing solid-phase extraction column, after drip washing finishes, the mixed solution of 5mL (methyl alcohol: the wash-out of glacial acetic acid=95:5v/v/v) again, eluent dries up with high pure nitrogen, then redissolving and use aperture with the 0.2mL methylene chloride is the membrane filtration of 0.22 μ m, gets the filtrate air inlet analysis of hplc of 1 μ L; , take nine kinds of organophosphorus pesticide concentration of standard solution as horizontal ordinate,, take chromatographic peak area as ordinate, draw respectively nine kinds of organophosphorus pesticide typical curves.
B. gas chromatographic detection:
The GC-2010FPD detecting device; Chromatographic column: RTX-1 (the neutral capillary column of 30.0m * 250 μ m * 0.1 μ m); Column temperature: 50 ℃, stop 1.0min, with 20 ℃ of min
-1Speed rising to 200 ℃, stop 10.0min, then with 40 ℃ of min
-1Speed rising to 240 ℃, stop 10.0min, altogether 32min.Injector temperature: 180 ℃, the FPD detector temperature: 250 ℃, carrier gas is high pure nitrogen, total flow: 6.6mL min
-1, post flow: 1.0mL min
-1, purge flow rate: 3.0mL min
-1, tail wind drift amount: 30.0mL min
-1, pressure: 39.4kPa, sample size: 1 μ L, split ratio: 2:1.
3. take 2.0g orange sample and carry out step 2) operation, determine in orange only to contain parathion-methyl and malathion according to resulting gas chromatogram.According to the gas chromatogram peak area, obtaining in orange the content of parathion-methyl and malathion by typical curve is respectively 0.016 and 0.024mg L
-1
Claims (1)
1. method that detects simultaneously nine kinds of organophosphorus pesticides is characterized in that comprising the following steps:
1) the 10mmoL 4-Aminobutanoicacid adds 5-20mL 2.5mol L
-1NaOH solution, ice bath stirs 30min; Then dropwise add 1-2mL o, the o-dimethyl thiophosphoryl chloride, regulate pH value to 10, and room temperature continues to stir 6h; Washing impurity is regulated pH to 2.0, then uses the ethyl acetate extraction potpourri; Revolve steaming, obtain common template 4-dimethoxy thiophosphoryl aminobutyric acid;
In acetonitrile solution, 4-dimethoxy thiophosphoryl aminobutyric acid, function monomer acrylamide, crosslinking chemical ethylene glycol dimethacrylate are mixed with the molar ratio of 1:3:8, then add azoisobutyronitrile to carry out polyreaction as initiating agent; The polymkeric substance that obtains is ground the rear methyl alcohol/glacial acetic acid 9:1v/v mixed solution continuous extraction 8h of using, then use 100% methanol extraction 4h, obtain molecularly imprinted polymer after drying;
2) will be added with the sample 2-4g of nine kinds of organophosphorus pesticide standard solution and the molecularly imprinted polymer mixed grinding of 0.5-1.0g step 1) preparation sample is scattered in molecularly imprinted polymer fully, said mixture will be filled in empty solid-phase extraction column; First use 30mL normal hexane drip washing solid-phase extraction column, it is methyl alcohol with the methyl alcohol glacial acetic acid mixed solution of 5mL again: glacial acetic acid=95:5v/v wash-out, the wash-out liquid nitrogen blows the rear 0.2mL of using methylene chloride and redissolves and filter, and gets the filtrate air inlet chromatography analysis of 1 μ L, the Criterion curve;
3) with testing sample repeating step 2) operation, calculated the content of metrifonate in testing sample, acephatemet, orthene, flolimat, Azodrin, Rogor, phosphamidon, parathion-methyl and malathion by typical curve according to the peak area of gas chromatography.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310352371.1A CN103399099B (en) | 2013-08-14 | 2013-08-14 | Method for detecting nine organophosphorus pesticides simultaneously |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310352371.1A CN103399099B (en) | 2013-08-14 | 2013-08-14 | Method for detecting nine organophosphorus pesticides simultaneously |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103399099A true CN103399099A (en) | 2013-11-20 |
| CN103399099B CN103399099B (en) | 2014-08-06 |
Family
ID=49562762
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310352371.1A Expired - Fee Related CN103399099B (en) | 2013-08-14 | 2013-08-14 | Method for detecting nine organophosphorus pesticides simultaneously |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103399099B (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104360000A (en) * | 2014-11-20 | 2015-02-18 | 山东农业大学 | Method for simultaneously detecting three organophosphorus pesticides |
| CN105348437A (en) * | 2015-10-27 | 2016-02-24 | 成都市食品药品检验研究院 | Dual-template molecularly imprinted polymer, and preparation method and application thereof |
| CN105699516A (en) * | 2016-01-27 | 2016-06-22 | 新会出入境检验检疫局综合技术服务中心 | Determination method of pesticides including ethoprophos in Xinhui tangerine peels and products of Xinhui tangerine peels |
| CN105699515A (en) * | 2016-01-27 | 2016-06-22 | 新会出入境检验检疫局综合技术服务中心 | Determination method of pesticides including dimethoate in Xinhui tangerine peels and products of Xinhui tangerine peels |
| CN105866320A (en) * | 2016-06-03 | 2016-08-17 | 四川大学 | Organophosphorus pesticide dimethoate residue detection method based on silica gel plate chromatography |
| CN106483218A (en) * | 2016-09-30 | 2017-03-08 | 山东农业大学 | A kind of molecular engram solid phase extraction liquid chromatograph detects metrifonate and Azodrin method simultaneously |
| CN109270033A (en) * | 2018-09-10 | 2019-01-25 | 南京市产品质量监督检验院 | The rapid detection method of Hazard factor in a kind of food |
| CN109655365A (en) * | 2018-12-29 | 2019-04-19 | 江苏微谱检测技术有限公司 | The detection method of organic agricultural chemicals in a kind of soil |
| CN109781899A (en) * | 2019-03-08 | 2019-05-21 | 无锡微色谱生物科技有限公司 | A method of using the screening of gas chromatography tandem mass spectrometry method and measurement green onion, ginger, 54 kinds of pesticide multi-residues in garlic |
| CN114689744A (en) * | 2022-03-21 | 2022-07-01 | 江南大学 | Application of functionalized three-dimensional covalent organic framework in detection of organophosphorus pesticide residues |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1635000A (en) * | 2004-12-28 | 2005-07-06 | 中国农业大学 | Molecular engram polyaromatics of organophosphorus parasiticide, method for preparation and application |
| CN101799460A (en) * | 2010-04-28 | 2010-08-11 | 中国烟草总公司郑州烟草研究院 | Method for detecting organophosphorus pesticide residue in tobacco |
-
2013
- 2013-08-14 CN CN201310352371.1A patent/CN103399099B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1635000A (en) * | 2004-12-28 | 2005-07-06 | 中国农业大学 | Molecular engram polyaromatics of organophosphorus parasiticide, method for preparation and application |
| CN101799460A (en) * | 2010-04-28 | 2010-08-11 | 中国烟草总公司郑州烟草研究院 | Method for detecting organophosphorus pesticide residue in tobacco |
Non-Patent Citations (3)
| Title |
|---|
| XIAOLAN ZHU等: "Selective solid-phase extraction using molecularly imprinted polymer for the analysis of polar organophosphorus pesticides in water and soil samples", 《JOURNAL OF CHROMATOGRAPHY A》, vol. 1092, no. 2, 15 August 2005 (2005-08-15), pages 161 - 169 * |
| 李建科等: "基质固相分散萃取气相色谱法检测苹果浓缩汁中5种有机磷农药的残留", 《南京农业大学学报》, vol. 28, no. 2, 31 December 2005 (2005-12-31), pages 111 - 115 * |
| 马昌等: "马拉硫磷分子印迹聚合物的制备及其在固相萃取中的应用", 《分析试验室》, vol. 30, no. 7, 31 July 2011 (2011-07-31), pages 58 - 61 * |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104360000A (en) * | 2014-11-20 | 2015-02-18 | 山东农业大学 | Method for simultaneously detecting three organophosphorus pesticides |
| CN105348437A (en) * | 2015-10-27 | 2016-02-24 | 成都市食品药品检验研究院 | Dual-template molecularly imprinted polymer, and preparation method and application thereof |
| CN105348437B (en) * | 2015-10-27 | 2017-11-24 | 成都市食品药品检验研究院 | A kind of double-template molecularly imprinted polymer and preparation method and application |
| CN105699515A (en) * | 2016-01-27 | 2016-06-22 | 新会出入境检验检疫局综合技术服务中心 | Determination method of pesticides including dimethoate in Xinhui tangerine peels and products of Xinhui tangerine peels |
| CN105699516A (en) * | 2016-01-27 | 2016-06-22 | 新会出入境检验检疫局综合技术服务中心 | Determination method of pesticides including ethoprophos in Xinhui tangerine peels and products of Xinhui tangerine peels |
| CN105699516B (en) * | 2016-01-27 | 2018-03-13 | 新会出入境检验检疫局综合技术服务中心 | The assay method of the agricultural chemicals such as phonamiphos in a kind of Xinhui tangerine peel and product |
| CN105699515B (en) * | 2016-01-27 | 2018-03-13 | 新会出入境检验检疫局综合技术服务中心 | The assay method of the agricultural chemicals such as Rogor in a kind of Xinhui tangerine peel and product |
| CN105866320A (en) * | 2016-06-03 | 2016-08-17 | 四川大学 | Organophosphorus pesticide dimethoate residue detection method based on silica gel plate chromatography |
| CN106483218A (en) * | 2016-09-30 | 2017-03-08 | 山东农业大学 | A kind of molecular engram solid phase extraction liquid chromatograph detects metrifonate and Azodrin method simultaneously |
| CN109270033A (en) * | 2018-09-10 | 2019-01-25 | 南京市产品质量监督检验院 | The rapid detection method of Hazard factor in a kind of food |
| CN109655365A (en) * | 2018-12-29 | 2019-04-19 | 江苏微谱检测技术有限公司 | The detection method of organic agricultural chemicals in a kind of soil |
| CN109655365B (en) * | 2018-12-29 | 2021-03-12 | 江苏微谱检测技术有限公司 | Method for detecting organic pesticide in soil |
| CN109781899A (en) * | 2019-03-08 | 2019-05-21 | 无锡微色谱生物科技有限公司 | A method of using the screening of gas chromatography tandem mass spectrometry method and measurement green onion, ginger, 54 kinds of pesticide multi-residues in garlic |
| CN114689744A (en) * | 2022-03-21 | 2022-07-01 | 江南大学 | Application of functionalized three-dimensional covalent organic framework in detection of organophosphorus pesticide residues |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103399099B (en) | 2014-08-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103399099B (en) | Method for detecting nine organophosphorus pesticides simultaneously | |
| CN102532390B (en) | Triazine weedicide, and metabolite molecular engram polymer microspheres, preparation method and application thereof | |
| Chen et al. | Molecularly imprinted polymer for the specific solid-phase extraction of kirenol from Siegesbeckia pubescens herbal extract | |
| CN101768238B (en) | Citrinin molecular engram material and preparation method as well as application thereof | |
| CN103901129A (en) | Method for detecting ten types of organophosphorus pesticides by using magnetic separation-gas chromatography | |
| CN102371084A (en) | Dibutyl phthalate molecularly imprinted polymer (DBP-MIP) solid phase extraction column and preparation method and application thereof | |
| CN102372821A (en) | Dibutyl phthalate molecularly imprinted polymer (DBP-MIP) and preparation method thereof | |
| CN104151489A (en) | Hydrophilic hydroxyl polychlorinated biphenyl molecularly imprinted solid-phase extraction filler as well as preparation method and application thereof | |
| CN104083904B (en) | Functionalization porous zinc sulfide nano microballoon solid-phase extraction column and preparation method thereof | |
| CN102174148A (en) | Preparation of triazine phytocide molecular imprinting solid phase extracting material | |
| CN103149308A (en) | Pretreatment method for detecting BPA (bisphenol A) in environment samples | |
| CN104568562A (en) | Water sample and pretreatment method of nitrosoamine compound in suspended matter of water sample | |
| CN105017465A (en) | Magnetic carbon nano tube surface molecularly imprinted polymer for benzo (a) pyrene and application thereof | |
| CN106582066A (en) | Cinnamate type ultraviolet sun-screening agent molecular engram solid-phase extraction column as well as preparation and application thereof | |
| CN103301820A (en) | Core-shell type Rhodamine B molecular imprinting solid-phase extraction magnetic material, and preparation method and application thereof | |
| CN102507820B (en) | Method for detecting trichlorfon and monocrotophos | |
| CN103396512B (en) | The preparation method and application of hybrid template molecularly imprinted polymer and solid-phase extraction column thereof | |
| CN102731706B (en) | Carbofuran molecularly imprinted microspheres, preparation and application thereof | |
| CN104569195B (en) | A kind of method of flavonoids effective constituent content in toothpaste detected containing baikal skullcap root | |
| CN103626938B (en) | A kind of preparation method of mezlocillin sodium silica gel surface molecularly imprinted polymer | |
| CN102749404B (en) | Method for detecting N-methyl carbamate pesticide residues | |
| CN101914066B (en) | Method for purifying and detecting pirimicarb by utilizing molecularly imprinted polymer (MIP) | |
| CN102507802A (en) | Extraction method for residual pyrethroid pesticides in water environment | |
| CN102565243B (en) | Method for preparing organic arsines molecular imprinting monolithic column and application thereof | |
| CN101317935A (en) | Rujietai formulation and quality detection method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20140806 Termination date: 20200814 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |