CN103983723B - Iminoctadine residues detection method in fruit and vegetable - Google Patents
Iminoctadine residues detection method in fruit and vegetable Download PDFInfo
- Publication number
- CN103983723B CN103983723B CN201410209344.3A CN201410209344A CN103983723B CN 103983723 B CN103983723 B CN 103983723B CN 201410209344 A CN201410209344 A CN 201410209344A CN 103983723 B CN103983723 B CN 103983723B
- Authority
- CN
- China
- Prior art keywords
- minutes
- solution
- efflux
- water
- add
- 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
Landscapes
- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
Abstract
The invention discloses a kind of iminoctadine residues detection method in fruit and vegetable, sample is adopted chemical reagent extracts, the little column purification of the silylated silica gel of ethyloic obtains testing liquid, Liquid Chromatography-Tandem Mass Spectrometry combined instrument is used to detect, the accuracy that the present invention has can be shortened sense cycle, improve testing result, reduces the feature of detection limit.
Description
Technical field
The invention belongs to technical field of food detection, especially relate to a kind of iminoctadine residues detection method in fruit and vegetable.
Background technology
Iminoctadine is widely used agricultural chemicals in the world, and various countries are all provided with strict residual benchmark in fruit and vegetable; The domestic report that there is no this type of detection method at present, has the report of the high performance liquid chromatograph using band post-column derivation fluorescence detector in the world, but this Comparison between detecting methods trouble.
Summary of the invention
The object of the invention is to improve prior art and a kind of accuracy can shortened sense cycle, improve testing result is provided, reduce the detection method of iminoctadine residual quantity in the fruit and vegetable of detection limit.
The object of the present invention is achieved like this, and iminoctadine residues detection method in fruit and vegetable, is characterized in that the method comprises the following steps:
A, extraction:
Accurately take 100.0g sample, add 25g guanidine hydrochloride, 100mL triethylamine solution, blend after mixing, take said mixture 1/5th amount, add 5g sodium chloride, 100mL normal butyl alcohol: normal hexane volume ratio is the mixed solution of 1:1, stir after 3 minutes, with 3000 turns of centrifugings per minute 10 minutes, being moved into by supernatant is equipped with in the 300mL separating funnel of 50mL triethylamine in advance, 50mL normal butyl alcohol is added: normal hexane volume ratio is the mixed solution of 1:1 in precipitation, stir after 3 minutes with 3000 turns of centrifugings per minute 10 minutes, merge supernatant in separating funnel, after shaking up, leave standstill, discard water layer, in above-mentioned separating funnel, add the 1mol/L sulfuric acid of 30mL water and 2mL, with the vibration of oscillator fierceness after 5 minutes, leave standstill, combining water layer is in ground decompression concentrator, the 1mol/L sulfuric acid of 20mL water and 0.5mL is added in the mixed solution layer of normal butyl alcohol and normal hexane, with the vibration of oscillator fierceness after 5 minutes, leave standstill, combining water layer is in decompression concentrator, less than 50 DEG C are concentrated into about 2mL, after adding the phosphate buffer of 5mLpH=6 in residue, add 0.1mol/L sodium hydroxide solution and regulate pH to be 6,
B, purification:
In the silylated silica gel pillar of the ethyloic of 1000mg, inject 10mL methyl alcohol, discard efflux, reinject 10mL water, discards efflux, injects after a step extracting method obtains solution, discard efflux in post; Reinject the phosphate buffer of 5mLpH=6, discards efflux, injects 10mL0.1mol/L methanol hydrochloride solution, collects efflux in ground decompression concentrator, below 40 DEG C, and removing hydrochloric acid and methyl alcohol, residue acetonitrile constant volume 2mL, this is testing liquid;
C, detection:
Use instrument: Liquid Chromatography-Tandem Mass Spectrometry combined instrument (LC-MS-MS);
INSTRUMENT MODEL: liquid chromatograph (LC): Agilent1200;
Tandem mass spectrometer (MS-MS): Agilent6410;
Liquid chromatography (LC) running parameter: chromatographic column: AgilentSB-C81.8 μm 2.1 × 150mm
Column temperature: 50 DEG C;
Flow velocity: 0.3mL/min;
Sample size: 10 μ L;
Arboxylic acid aqueous ammonium: draw 1mL formic acid solution, then take 0.75g ammonium acetate, be diluted with water to 1000mL;
Mobile phase and elution requirement: 40% acetonitrile and 60% arboxylic acid aqueous ammonium Gradient elution;
Tandem mass spectrum (MS-MS) running parameter: capillary voltage: 4000V; Ion source temperature: 350 DEG C; Desolventizing air-flow: 10L/min; Scan mode: positive ion scans; Detection mode: multiple-reaction monitoring (MRM); Parent ion 357, daughter ion 272,323; Quantitative limit: 0.005mg/kg.
Compared with the prior art the present invention has following distinguishing feature and good effect:
1, in extraction link, add guanidine hydrochloride and triethylamine in leaching process, triethylamine solution can the silanol group of privacy glass utensil, avoids iminoctadine and is attracted on glassware; Adding guanidine hydrochloride can prevent iminoctadine from being adsorbed by plant component; Add the recovery that these two kinds of materials can improve iminoctadine greatly, improve the recovery 30% relative to traditional detection method, also just improve the accuracy of testing result.
2, detection employs Liquid Chromatography-Tandem Mass Spectrometry instrument (LC-MS-MS), advantage does not need to carry out post-column derivation, directly can detect, substantially reduce sense cycle, Liquid Chromatography-Tandem Mass Spectrometry instrument is more advanced equipment simultaneously, greatly reduces detection limit.With green grass or young crops stalk dish for product to be tested, detect in the conventional way, detecting iminoctadine content is 0.024mg/kg, be 0.040mg/kg as carried out the result after recovery correction, detect a sample required time 5h, detect with this method, it is 0.042mg/kg that same sample detects iminoctadine content, detects a sample required time 2.5h; Detection limit reduces, and for grape, (0.02mg/kg) detection limit in the conventional way, testing result is not for detect (lower than detection limit), and detect with this method, testing result is 0.009mg/kg.
The accuracy of the inventive method, precision and detection limit are analyzed as follows:
In green grass or young crops stalk dish, grape, add 0.02mg/kg, 0.05mg/kg, 0.10mg/kg standard sample of pesticide respectively do interpolation recovery, each contents level repeats 3 times, the average recovery rate of the iminoctadine obtained and relative standard deviation: when Pitch-based sphere is within the scope of 0.02 ~ 0.10mg/kg, the agricultural chemicals recovery is 91% ~ 98%, relative standard deviation is 3.6 ~ 5.4%, n=3, the recovery and relative standard deviation all meet the residual testing requirement of agriculture, agricultural chemicals minimum detectability is 0.005mg/kg, and concrete data are as following table:
Table 1 green grass or young crops stalk dish average recovery rate and relative standard deviation n=3
Table 2 grape average recovery rate and relative standard deviation n=3
Accompanying drawing explanation
Below in conjunction with drawings and Examples, the present invention is described in further detail.
Fig. 1 is iminoctadine standard items chromatograms.
Fig. 2 is that blue or green stalk dish adds recovery chromatogram.
Embodiment
Embodiment 1, iminoctadine residues detection method in fruit and vegetable, this example is with green grass or young crops stalk dish for product to be tested detects, and step is as follows:
Accurately take the green grass or young crops stalk dish sample of 100.0g, add 25g guanidine hydrochloride, 100mL triethylamine solution, blend after mixing, take said mixture 1/5th amount, add 5g sodium chloride, 100mL normal butyl alcohol: normal hexane volume ratio is the mixed solution of 1:1, stir after 3 minutes, with 3000 turns of centrifugings per minute 10 minutes, being moved into by supernatant is equipped with in the 300mL separating funnel of 50mL triethylamine in advance, 50mL normal butyl alcohol is added: normal hexane volume ratio is the mixed solution of 1:1 in precipitation, stir after 3 minutes with 3000 turns of centrifugings per minute 10 minutes, merge supernatant in separating funnel, after shaking up, leave standstill, discard water layer, in above-mentioned separating funnel, add the 1mol/L sulfuric acid of 30mL water and 2mL, with the vibration of oscillator fierceness after 5 minutes, leave standstill, combining water layer is in ground decompression concentrator, the 1mol/L sulfuric acid of 20mL water and 0.5mL is added in the mixed solution layer of normal butyl alcohol and normal hexane, with the vibration of oscillator fierceness after 5 minutes, leave standstill, combining water layer is in decompression concentrator, less than 50 DEG C are concentrated into about 2mL, after adding the phosphate buffer of 5mLpH=6 in residue, add 0.1mol/L sodium hydroxide solution and regulate pH to be 6, this is solution to be clean.In the silylated silica gel pillar of the ethyloic of 1000mg, inject 10mL methyl alcohol, discard efflux, reinject 10mL water, discards efflux, injects solution to be clean, discard efflux in post; Reinject the phosphate buffer of 5mLpH=6, discards efflux, injects 10mL0.1mol/L methanol hydrochloride solution, collects efflux in ground decompression concentrator, and below 40 DEG C, removing hydrochloric acid and methyl alcohol, residue acetonitrile constant volume 2mL, this is for detecting solution.Liquid Chromatography-Tandem Mass Spectrometry combined instrument (LC-MS-MS) is used to detect, INSTRUMENT MODEL: liquid chromatograph (LC): Agilent1200; Tandem mass spectrometer (MS-MS): Agilent6410; Liquid chromatography (LC) running parameter: chromatographic column: AgilentSB-C81.8 μm 2.1 × 150mm; Column temperature: 50 DEG C; Flow velocity: 0.3mL/min; Sample size: 10 μ L; Arboxylic acid aqueous ammonium: draw 1mL formic acid solution, then take 0.75g ammonium acetate, be diluted with water to 1000mL; Mobile phase and elution requirement: 40% acetonitrile and 60% arboxylic acid aqueous ammonium Gradient elution; Tandem mass spectrum (MS-MS) running parameter: capillary voltage: 4000V; Ion source temperature: 350 DEG C; Desolventizing air-flow: 10L/min; Scan mode: positive ion scans; Detection mode: multiple-reaction monitoring (MRM); Parent ion 357, daughter ion 272,323.
This testing sample classic method detects, it is 0.024mg/kg that sample detects iminoctadine content, result after the recovery corrects is 0.040mg/kg, value is detected for 0.042mg/kg according to the present embodiment detection method, above-mentioned example explanation, this detection method without significant difference, illustrates that this method obtains one well quantitatively in testing result.
Embodiment 2, iminoctadine residues detection method in fruit and vegetable, this example is that product to be tested detects with grape, and step is as follows:
Accurately take the grape sample of 100.0g, add 25g guanidine hydrochloride, 100mL triethylamine solution, blend after mixing, take said mixture 1/5th amount, add 5g sodium chloride, 100mL normal butyl alcohol: normal hexane volume ratio is the mixed solution of 1:1, stir after 3 minutes, with 3000 turns of centrifugings per minute 10 minutes, being moved into by supernatant is equipped with in the 300mL separating funnel of 50mL triethylamine in advance, 50mL normal butyl alcohol is added: normal hexane volume ratio is the mixed solution of 1:1 in precipitation, stir after 3 minutes with 3000 turns of centrifugings per minute 10 minutes, merge supernatant in separating funnel, after shaking up, leave standstill, discard water layer, in above-mentioned separating funnel, add the 1mol/L sulfuric acid of 30mL water and 2mL, with the vibration of oscillator fierceness after 5 minutes, leave standstill, combining water layer is in ground decompression concentrator, the 1mol/L sulfuric acid of 20mL water and 0.5mL is added in the mixed solution layer of normal butyl alcohol and normal hexane, with the vibration of oscillator fierceness after 5 minutes, leave standstill, combining water layer is in decompression concentrator, less than 50 DEG C are concentrated into about 2mL, after adding the phosphate buffer of 5mLpH=6 in residue, add 0.1mol/L sodium hydroxide solution and regulate pH to be 6, this is solution to be clean.In the silylated silica gel pillar of the ethyloic of 1000mg, inject 10mL methyl alcohol, discard efflux, reinject 10mL water, discards efflux, injects solution to be clean, discard efflux in post; Reinject the phosphate buffer of 5mLpH=6, discards efflux, injects 10mL0.1mol/L methanol hydrochloride solution, collects efflux in ground decompression concentrator, and below 40 DEG C, removing hydrochloric acid and methyl alcohol, residue acetonitrile constant volume 2mL, this is for detecting solution.Liquid Chromatography-Tandem Mass Spectrometry combined instrument (LC-MS-MS) is used to detect, INSTRUMENT MODEL: liquid chromatograph (LC): Agilent1200; Tandem mass spectrometer (MS-MS): Agilent6410; Liquid chromatography (LC) running parameter: chromatographic column: AgilentSB-C81.8 μm 2.1 × 150mm; Column temperature: 50 DEG C; Flow velocity: 0.3mL/min; Sample size: 10 μ L; Arboxylic acid aqueous ammonium: draw 1mL formic acid solution, then take 0.75g ammonium acetate, be diluted with water to 1000mL; Mobile phase and elution requirement: 40% acetonitrile and 60% arboxylic acid aqueous ammonium Gradient elution; Tandem mass spectrum (MS-MS) running parameter: capillary voltage: 4000V; Ion source temperature: 350 DEG C; Desolventizing air-flow: 10L/min; Scan mode: positive ion scans; Detection mode: multiple-reaction monitoring (MRM); Parent ion 357, daughter ion 272,323.
This testing sample classic method detects, sample does not detect iminoctadine, detects value for 0.009mg/kg, above-mentioned example explanation according to the present embodiment detection method, this detection method is better than classic method on detection limit, illustrates that this method has lower quantitative limit.
Above-described example is only be described the specific embodiment of the present invention, not limits scope of the present invention.
Claims (1)
1. iminoctadine residues detection method in fruit and vegetable, is characterized in that the method comprises the following steps:
A, extraction:
Accurately take 100.0g sample, add 25g guanidine hydrochloride, 100mL triethylamine solution, blend after mixing, take said mixture 1/5th amount, add 5g sodium chloride, 100mL normal butyl alcohol: normal hexane volume ratio is the mixed solution of 1:1, stir after 3 minutes, with 3000 turns of centrifugings per minute 10 minutes, being moved into by supernatant is equipped with in the 300mL separating funnel of 50mL triethylamine in advance, 50mL normal butyl alcohol is added: normal hexane volume ratio is the mixed solution of 1:1 in precipitation, stir after 3 minutes with 3000 turns of centrifugings per minute 10 minutes, merge supernatant in separating funnel, after shaking up, leave standstill, discard water layer, in above-mentioned separating funnel, add the 1mol/L sulfuric acid of 30mL water and 2mL, after 5 minutes with the vibration of oscillator fierceness, leave standstill, water layer is moved in ground decompression concentrator, the 1mol/L sulfuric acid of 20mL water and 0.5mL is added in the mixed solution layer of normal butyl alcohol and normal hexane, with the vibration of oscillator fierceness after 5 minutes, leave standstill, combining water layer is in ground decompression concentrator, less than 50 DEG C are concentrated into about 2mL, after adding the phosphate buffer of 5mLpH=6 in residue, add 0.1mol/L sodium hydroxide solution and regulate pH to be 6, this is solution to be clean,
B, purification:
In the silylated silica gel pillar of the ethyloic of 1000mg, inject 10mL methyl alcohol, discard efflux, reinject 10mL water, discards efflux, injects after a step extracting method obtains solution to be clean, discard efflux in post; Reinject the phosphate buffer of 5mLpH=6, discards efflux, injects 10mL0.1mol/L methanol hydrochloride solution, collects efflux in ground decompression concentrator, below 40 DEG C, and removing hydrochloric acid and methyl alcohol, residue acetonitrile constant volume 2mL, this is testing liquid;
C, detection:
Use instrument: Liquid Chromatography-Tandem Mass Spectrometry combined instrument (LC-MS-MS);
INSTRUMENT MODEL: liquid chromatograph (LC): Agilent1200;
Tandem mass spectrometer (MS-MS): Agilent6410;
Liquid chromatography (LC) running parameter: chromatographic column: AgilentSB-C81.8 μm 2.1 × 150mm
Column temperature: 50 DEG C;
Flow velocity: 0.3mL/min;
Sample size: 10 μ L;
Arboxylic acid aqueous ammonium: draw 1mL formic acid solution, then take 0.75g ammonium acetate, be diluted with water to 1000mL;
Mobile phase and elution requirement: 40% acetonitrile and 60% arboxylic acid aqueous ammonium Gradient elution;
Tandem mass spectrum (MS-MS) running parameter: capillary voltage: 4000V; Ion source temperature: 350 DEG C; Desolventizing air-flow: 10L/min; Scan mode: positive ion scans; Detection mode: multiple-reaction monitoring (MRM); Parent ion 357, daughter ion 272,323; Quantitative limit: 0.005mg/kg.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410209344.3A CN103983723B (en) | 2014-05-19 | 2014-05-19 | Iminoctadine residues detection method in fruit and vegetable |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410209344.3A CN103983723B (en) | 2014-05-19 | 2014-05-19 | Iminoctadine residues detection method in fruit and vegetable |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103983723A CN103983723A (en) | 2014-08-13 |
| CN103983723B true CN103983723B (en) | 2015-12-30 |
Family
ID=51275775
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410209344.3A Active CN103983723B (en) | 2014-05-19 | 2014-05-19 | Iminoctadine residues detection method in fruit and vegetable |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103983723B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105021436B (en) * | 2015-07-18 | 2018-09-04 | 福建省测试技术研究所 | A kind of pesticide extracting solution and its application |
| KR102061600B1 (en) * | 2018-06-12 | 2020-01-09 | 대한민국 | Method of analyzing pesticide residues of imminoctadine in agricultural products |
| CN113419022B (en) * | 2021-06-17 | 2023-03-07 | 南宁海关技术中心 | Method for measuring residual quantity of iminoctadine in plant-derived food by solid phase extraction-liquid chromatography-tandem mass spectrometry |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN86105582A (en) * | 1985-07-23 | 1987-01-21 | 大日本油墨化学工业株式会社 | 1,1 '-preparation method of imino--two (eight methylene radical)-biguanides 3-alkylbenzene sulfonate |
| CN102375034A (en) * | 2010-08-17 | 2012-03-14 | 贾明宏 | Guanidine-benzoin derivative reaction and application of guanidine-benzoin derivative reaction in rapid detection by high performance liquid chromatography |
| WO2014056780A1 (en) * | 2012-10-12 | 2014-04-17 | Basf Se | A method for combating phytopathogenic harmful microbes on cultivated plants or plant propagation material |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06234608A (en) * | 1993-02-10 | 1994-08-23 | Sankei Kagaku Kk | Phytotoxicity reducing agent |
-
2014
- 2014-05-19 CN CN201410209344.3A patent/CN103983723B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN86105582A (en) * | 1985-07-23 | 1987-01-21 | 大日本油墨化学工业株式会社 | 1,1 '-preparation method of imino--two (eight methylene radical)-biguanides 3-alkylbenzene sulfonate |
| CN102375034A (en) * | 2010-08-17 | 2012-03-14 | 贾明宏 | Guanidine-benzoin derivative reaction and application of guanidine-benzoin derivative reaction in rapid detection by high performance liquid chromatography |
| WO2014056780A1 (en) * | 2012-10-12 | 2014-04-17 | Basf Se | A method for combating phytopathogenic harmful microbes on cultivated plants or plant propagation material |
Non-Patent Citations (7)
| Title |
|---|
| Analysis of guazatine mixture by LC and LC–MS and antimycotic activity determination of principal components;Elena Dreassi et al.;《Journal of Pharmaceutical and Biomedical Analysis》;20061201;第43卷;第1499页第1-2段，第1500页"2.Experimental"节，第1503页Fig 3，第1504页 Table 2，第1505页右栏第2-3段 * |
| LC/ESI/MS Method for the Quantitative Detection of Guazatine Residues in Cereals;ELENA DREASS et al.;《J. Agric. Food Chem.》;20070725;第55卷;Page 6850-6856 * |
| LC/MS/MS detection of fungicide guazatine residues for quality assessment of commercial citrus fruit;Monica Scordino et al.;《Eur Food Res Technol》;20080311;第227卷;Page 1339–1347 * |
| 抑霉唑和双胍辛胺在浙江柑桔中的降解与残留;李振 等;《浙江农业学报》;20001231;第12卷(第6期);397-399页 * |
| 新杀菌剂——双辛胍胺(guazatine);日本《植物防疫》编辑部;《农药译丛》;19841231;第6卷(第6期);61-62页 * |
| 高效液相色谱定量分析双胍三辛烷基苯磺酸盐40%可湿性粉剂;邹伟斌 等;《农药科学与管理》;20121231;第33卷(第1期);35-38页 * |
| 高效液相色谱法测定番茄与土壤中双胍三辛烷苯基磺酸盐残留量;吴珉 等;《农药》;20061130;第45卷(第11期);第775页"摘要"，第776页1.1-1.2节，1.4节 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103983723A (en) | 2014-08-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104215704B (en) | The method for quick of oligosaccharides in adulterated honey | |
| CN102735784B (en) | Method for simultaneously determining one hundred pesticide residuals in traditional Chinese medicine through ultrahigh performance liquid chromatography-tandem quadrupole mass spectrum | |
| CN102183611B (en) | Method for detecting pesticide residue in white paeony root crude drug | |
| JP2021512292A (en) | Triple quadrupole mass spectrometer configured to detect pesticide residue MRM transitions | |
| CN103983723B (en) | Iminoctadine residues detection method in fruit and vegetable | |
| CN104634897B (en) | A kind of method detecting cigarette mainstream flue gas middle and advanced stage advanced glycation end products | |
| Guan et al. | Modified QuEChERS method for the analysis of 11 pesticide residues in tea by liquid chromatography–tandem mass spectrometry | |
| CN107843664A (en) | The assay method of glufosinate-ammonium, glyphosate and its metabolin aminomethyl phosphonic acid residual quantity in tealeaves | |
| CN108226341B (en) | Method for accurately detecting pesticide residues in agricultural products | |
| CN105758946A (en) | Method for determining residual quantity of 15 kinds of triazole type pesticides in fruit | |
| CN104237402B (en) | Extracting and measuring method of perfluorinated compounds in bark and leaves | |
| CN105548431A (en) | Method for simultaneously detecting residual quantities of oxamyl and oxamyl oxime in vegetable/fruits | |
| CN105372353A (en) | Method for detecting residual quantities of glyphosate and phosphonic acid being metabolite of glyphosate in food | |
| CN105891374A (en) | Detection method for measuring eight preservatives in reconstituted tobaccos simultaneously | |
| CN103293260B (en) | Method for high-efficiency detection of rhodamine B in food and rapid detection kit | |
| CN111380980A (en) | Method for detecting pesticide residue on fruits and vegetables | |
| CN102580351A (en) | Series solid-phase extraction (SPE) method for nitrosamine compounds in drinking water | |
| CN105866315B (en) | The assay method of amino acid in a kind of tobacco juice for electronic smoke | |
| CN101334386B (en) | Determination method for plant medicine blood plasma amygdalin for strengthening the body resistance | |
| CN108445128B (en) | Method for measuring residual amount of carbamate drugs in eggs | |
| CN106404507A (en) | Leaf vegetable gibberellins residue detection sample pretreatment method and detection method | |
| CN110596276A (en) | Method for measuring dithiocarbamate residues in tea leaves by headspace-gas chromatography-mass spectrometry | |
| CN103962114B (en) | The preparation method of electroconductive polymer coating silica gel and the application in SPE thereof | |
| CN116908317A (en) | Method for detecting food additives in four types of wines | |
| CN106290662A (en) | Organochlorine pesticide and the method for quick of pyrethroid pesticide and pre-treating method thereof in Folium Camelliae sinensis |
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 | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: Method for determination of biguanide octylamine residues in fruits and vegetables Effective date of registration: 20211126 Granted publication date: 20151230 Pledgee: Yantai financing guarantee Group Co.,Ltd. Pledgor: LAIYANG HENGRUN FOODSTUFF Co.,Ltd. Registration number: Y2021370010130 |
|
| 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: 20230313 Granted publication date: 20151230 Pledgee: Yantai financing guarantee Group Co.,Ltd. Pledgor: LAIYANG HENGRUN FOODSTUFF Co.,Ltd. Registration number: Y2021370010130 |
|
| PC01 | Cancellation of the registration of the contract for pledge of patent right |