CN102353740A - Method for synchronous determination of content of triazole chiral pesticide enantiomers - Google Patents
Method for synchronous determination of content of triazole chiral pesticide enantiomers Download PDFInfo
- Publication number
- CN102353740A CN102353740A CN2011101488396A CN201110148839A CN102353740A CN 102353740 A CN102353740 A CN 102353740A CN 2011101488396 A CN2011101488396 A CN 2011101488396A CN 201110148839 A CN201110148839 A CN 201110148839A CN 102353740 A CN102353740 A CN 102353740A
- Authority
- CN
- China
- Prior art keywords
- enantiomorph
- azoles
- mass
- ion
- charge ratio
- 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
- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
Abstract
The invention discloses a method for synchronous determination of the content of triazole chiral pesticide enantiomers. According to the method, the technology of accelerated solvent extraction is used to treat a soil sample, an online polarimetric optical detector is used to determine the eluting sequence of the enantiomers, and the methods of reverse phase liquid chromatography with a chiral stationary phase and triple quadruple tandem mass spectrometry are utilized for synchronous determination of enantiomers of nine triazole chiral pesticides, namely, hexaconazole, flutriafol, diniconazole, cyproconazole, tetraconazole, epoxiconazole, myclobutanil, fenbuconazole and triadimefon; the detection limit of the method is as low as 0.5 to 1.0 mu g/kg.
Description
Technical field
The invention belongs to analytical chemistry field and Detecting Pesticide technical field, relate to a kind of method of synchronous mensuration triazole type chirality agricultural chemicals enantiomorph content.
Background technology
Possibly there is huge difference aspect activity, toxicity, absorption, degraded, metabolism and the elimination etc. of chirality agricultural chemicals enantiomorph in physical environment and biosome are many; The biologically active that shows such as two enantiomorphs is different often; Or even diametrically opposite: promptly an enantiomorph has good preventive and therapeutic effect to disease and pest; Another enantiomorph then activity is very little; Or do not have effect, even possibly produce stronger toxic and side effect.Be subjected to the influence of the market demand, economic benefit and environmental protection factor; The content that people also begin to adopt the single-activity enantiomorph or improve certain active enantiomorph; Improve prevention and control of plant diseases, pest control effect and obtain higher economic benefit, alleviate the pollution of agricultural chemicals simultaneously environment.Therefore, the research that is to the Separation of Enantiomers analysis of chirality agricultural chemicals and selective row becomes new focus, and correlative study progressively increases and deepens continuously.
The triazole type agricultural chemicals is one big type of chemical pesticide with chirality characteristic; Demonstrate the diverse living features of character between its enantiomorph; Bactericidal activity like R-alkene azoles alcohol is higher than the S-enantiomorph far away; And the plant growth regulating activity of S-enantiomorph is than R-mapping height, and this phenomenon shows more obviously on uniconazole P.(-)-enantiomorph bactericidal activity of the pure and mild Tebuconazole of own azoles all is higher than (+)-enantiomorph, and (+)-Flutriafol activity is higher than (-)-Flutriafol.Activity difference is very little between two enantiomorphs of triazolone, but its reduzate Triadimenol has four enantiomorphs, 1S wherein, and the 2R-enantiomorph has higher bactericidal activity.Aspect the residual and katabolism in environment and biosome, these agricultural chemicals also have bigger difference.In multiple soil, have the stereoselectivity degradation behavior like fluorine ring azoles and cyproconazole enantiomorph, there is the selectivity degraded in alkaline soils in cis fluorine ring azoles under the oxygen consumption condition, also exists the difference of degradation rate between four isomeride of Cyproconazole.After family's rabbit ear vein is injected own azoles alcohol raceme; Increase the concentration of (-)-own azoles alcohol in blood plasma in time obviously greater than its enantiomorph concentration; (+)-own azoles alcohol is also eliminated soon than (-)-own azoles alcohol in heart, liver, kidney, spleen and brain tissue, and the stereoselectivity behavior in liver is the most obvious.
Stereoselectivity behaviors such as the activity of research triazole type chirality agricultural chemicals enantiomorph, residual, degraded and metabolism just need split its enantiomorph, set up effective, sensitive Chiral Separation analytical approach.The method for splitting that appears in the newspapers at present is more, as on the positive liquid chromatography, can directly splitting multiple triazole bactericidal agents such as triazolone, own azoles alcohol, Tebuconazole with chirality OD (cellulose-3,5-3,5-dimethylphenyl carbamate) stationary phase; With germifuge such as the detachable triazolone of Sulfonated beta-schardinger dextrin-Capillary Electrophoresis, the pure and mild Tebuconazoles of own azoles.With commercial chirality AD post (amylose-3,5-3,5-dimethylphenyl carbamate) 6 kinds of triazole type agricultural chemicals such as detachable Tebuconazole, own azoles alcohol under the supercritical fluid chromatography condition.In these methods, liquid chromatography chiral stationary phase method is the most general and easy to operate, has obtained using widely.But existing liquid chromatography fado adopts normal-phase chromatography and UV-detector to carry out the analysis of enantiomorph, generally can only a kind of enantiomorph of chirality agricultural chemicals be separated and detect.Because UV-detector is a kind of common detector; Receive the interference of sample substrate easily during working sample and influence the selectivity of method; The sensitivity of this detecting device simultaneously is also relatively low, therefore separated in synchronization and the high-sensitivity detection that can't accomplish multiple chirality agricultural chemicals enantiomorph.
Summary of the invention
The method that the purpose of this invention is to provide a kind of synchronous mensuration triazole type chirality agricultural chemicals enantiomorph content.
Method of from sample, separating triazole type chirality agricultural chemicals enantiomorph provided by the invention comprises the steps:
Testing sample is carried out liquid chromatography-tandem mass spectrometry to be detected; Mass-to-charge ratio characteristic according to the parent ion/daughter ion of the mass-to-charge ratio of the parent ion/daughter ion of eluting peak retention time and detection by quantitative and qualitative detection is separated each eluting peak, promptly obtains each triazole type chirality agricultural chemicals enantiomorph;
Said triazole type chirality agricultural chemicals is selected from least a in the following compound: own azoles alcohol, Flutriafol, alkene azoles alcohol, Cyproconazole, fluorine ether azoles, fluorine ring azoles, nitrile bacterium azoles, RH-7592 and triazolone;
The condition of said liquid chromatographic detection is following: chromatographic column is for loading cellulose-3, the Phenomenex Lux Cellulose-1 chromatographic column of 5-3,5-dimethylphenyl carbamate stationary phase; The elution buffer that uses is the mixed solution of acetonitrile and water, and type of elution is a gradient elution, and elution speed is 0.3mL/min;
Said gradient elution mode is following:
1min rises to the 6min end, and the volume ratio of water and acetonitrile is 50%: 50% in the mixed solution;
7min rises to the 10min end, and the volume ratio of water and acetonitrile is 30%: 70% in the mixed solution;
11min rises to the 18min end, and the volume ratio of water and acetonitrile is 50%: 50% in the mixed solution;
The method that said mass-to-charge ratio characteristic according to eluting peak retention time and parent ion/daughter ion is separated each eluting peak is following:
Retention time is that 5.72 minutes, the mass-to-charge ratio of the parent ion/daughter ion of detection by quantitative are that the mass-to-charge ratio of the parent ion/daughter ion of 314.4/70.0 and qualitative detection is (+) enantiomorph that the eluting peak of 314.4/159.0 is own azoles alcohol;
Retention time is that 6.50 minutes, the mass-to-charge ratio of the parent ion/daughter ion of detection by quantitative are that the mass-to-charge ratio of the parent ion/daughter ion of 314.4/70.0 and qualitative detection is (-) enantiomorph that the eluting peak of 314.4/159.0 is own azoles alcohol;
Retention time is that 3.27 minutes, the mass-to-charge ratio of the parent ion/daughter ion of detection by quantitative are that the mass-to-charge ratio of the parent ion/daughter ion of 302.1/70.0 and qualitative detection is (-) enantiomorph that the eluting peak of 302.1/123.1 is Flutriafol;
Retention time is that 3.47 minutes, the mass-to-charge ratio of the parent ion/daughter ion of detection by quantitative are that the mass-to-charge ratio of the parent ion/daughter ion of 302.1/70.0 and qualitative detection is (+) enantiomorph that the eluting peak of 302.1/123.1 is Flutriafol;
Retention time is that 6.48 minutes, the mass-to-charge ratio of the parent ion/daughter ion of detection by quantitative are that the mass-to-charge ratio of the parent ion/daughter ion of 326.1/70.0 and qualitative detection is (-) enantiomorph that the eluting peak of 326.1/159.0 is alkene azoles alcohol;
Retention time is that 6.97 minutes, the mass-to-charge ratio of the parent ion/daughter ion of detection by quantitative are that the mass-to-charge ratio of the parent ion/daughter ion of 326.1/70.0 and qualitative detection is (-) enantiomorph that the eluting peak of 326.1/159.0 is alkene azoles alcohol;
Retention time is that 4.35 minutes, the mass-to-charge ratio of the parent ion/daughter ion of detection by quantitative are that the mass-to-charge ratio of the parent ion/daughter ion of 292.2/70.0 and qualitative detection is (+) enantiomorph that the eluting peak of 292.2/125.0 is Cyproconazole;
Retention time is that 5.10 minutes, the mass-to-charge ratio of the parent ion/daughter ion of detection by quantitative are that the mass-to-charge ratio of the parent ion/daughter ion of 292.2/70.0 and qualitative detection is (+) enantiomorph that the eluting peak of 292.2/125.0 is Cyproconazole;
Retention time is that 5.67 minutes, the mass-to-charge ratio of the parent ion/daughter ion of detection by quantitative are that the mass-to-charge ratio of the parent ion/daughter ion of 292.2/70.0 and qualitative detection is (-) enantiomorph that the eluting peak of 292.2/125.0 is Cyproconazole;
Retention time is that 12.51 minutes, the mass-to-charge ratio of the parent ion/daughter ion of detection by quantitative are that the mass-to-charge ratio of the parent ion/daughter ion of 292.2/70.0 and qualitative detection is (-) enantiomorph that the eluting peak of 292.2/125.0 is Cyproconazole;
Retention time is that 6.99 minutes, the mass-to-charge ratio of the parent ion/daughter ion of detection by quantitative are that the mass-to-charge ratio of the parent ion/daughter ion of 372.2/159.0 and qualitative detection is (+) enantiomorph that the eluting peak of 372.2/70.0 is fluorine ether azoles;
Retention time is that 8.52 minutes, the mass-to-charge ratio of the parent ion/daughter ion of detection by quantitative are that the mass-to-charge ratio of the parent ion/daughter ion of 372.2/159.0 and qualitative detection is (-) enantiomorph that the eluting peak of 372.2/70.0 is fluorine ether azoles;
Retention time is that 7.14 minutes, the mass-to-charge ratio of the parent ion/daughter ion of detection by quantitative are that the mass-to-charge ratio of the parent ion/daughter ion of 330.3/121.2 and qualitative detection is (-) enantiomorph that the eluting peak of 330.3/123.2 is fluorine ring azoles;
Retention time is that 11.59 minutes, the mass-to-charge ratio of the parent ion/daughter ion of detection by quantitative are that the mass-to-charge ratio of the parent ion/daughter ion of 330.3/121.2 and qualitative detection is (+) enantiomorph that the eluting peak of 330.3/123.2 is fluorine ring azoles;
Retention time is that 6.05 minutes, the mass-to-charge ratio of the parent ion/daughter ion of detection by quantitative are that the mass-to-charge ratio of the parent ion/daughter ion of 289.2/70.0 and qualitative detection is (+) enantiomorph that the eluting peak of 289.2/125.0 is nitrile bacterium azoles;
Retention time is that 7.77 minutes, the mass-to-charge ratio of the parent ion/daughter ion of detection by quantitative are that the mass-to-charge ratio of the parent ion/daughter ion of 289.2/70.0 and qualitative detection is (-) enantiomorph that the eluting peak of 289.2/125.0 is nitrile bacterium azoles;
Retention time is that 10.66 minutes, the mass-to-charge ratio of the parent ion/daughter ion of detection by quantitative are that the mass-to-charge ratio of the parent ion/daughter ion of 337.2/70.0 and qualitative detection is (+) enantiomorph that the eluting peak of 337.2/125.0 is RH-7592;
Retention time is that 11.66 minutes, the mass-to-charge ratio of the parent ion/daughter ion of detection by quantitative are that the mass-to-charge ratio of the parent ion/daughter ion of 337.2/70.0 and qualitative detection is (-) enantiomorph that the eluting peak of 337.2/125.0 is RH-7592;
Retention time is that 5.02 minutes, the mass-to-charge ratio of the parent ion/daughter ion of detection by quantitative are that the mass-to-charge ratio of the parent ion/daughter ion of 294.1/197.1 and qualitative detection is (-) enantiomorph that the eluting peak of 294.1/69.1 is triazolone;
Retention time is that 5.61 minutes, the mass-to-charge ratio of the parent ion/daughter ion of detection by quantitative are that the mass-to-charge ratio of the parent ion/daughter ion of 294.1/197.1 and qualitative detection is (+) enantiomorph that the eluting peak of 294.1/69.1 is triazolone.
In the testing conditions of the said liquid chromatography of said method, the length of said chromatographic column is 150 millimeters, and internal diameter is 2.0 millimeters; Sample size is 10 μ L; Said cellulose-3, the particle diameter of 5-3,5-dimethylphenyl carbamate are 3 μ m.
In the said Mass Spectrometer Method condition, electron spray ionisation source atomization gas pressure is 15psi, and dry gas is 55psi, and the collision atmospheric pressure is 3psi, and ionization voltage is+5500V, and ion source temperature is 400 ℃;
Every kind of enantiomorph is corresponding separates a bunch voltage, impact energy is following:
(+) enantiomorph of own azoles alcohol: separating bunch voltage is 25, and impact energy is 35;
(-) enantiomorph of own azoles alcohol: separating bunch voltage is 25, and impact energy is 35;
(-) enantiomorph of Flutriafol: separating bunch voltage is 25, and impact energy is 35;
(+) enantiomorph of Flutriafol: separating bunch voltage is 25, and impact energy is 35;
(-) enantiomorph of alkene azoles alcohol: separating bunch voltage is 25, and impact energy is 35;
(+) enantiomorph of alkene azoles alcohol: separating bunch voltage is 25, and impact energy is 35;
(+) enantiomorph of Cyproconazole: separating bunch voltage is 25, and impact energy is 35;
(+) enantiomorph of Cyproconazole: separating bunch voltage is 25, and impact energy is 35;
(-) enantiomorph of Cyproconazole: separating bunch voltage is 25, and impact energy is 35;
(-) enantiomorph of Cyproconazole: separating bunch voltage is 25, and impact energy is 35;
(+) enantiomorph of fluorine ether azoles: separating bunch voltage is 20, and impact energy is 30;
(-) enantiomorph of fluorine ether azoles: separating bunch voltage is 20, and impact energy is 35;
(-) enantiomorph of fluorine ring azoles: separating bunch voltage is 25, and impact energy is 30;
(+) enantiomorph of fluorine ring azoles: separating bunch voltage is 25, and impact energy is 30;
(+) enantiomorph of nitrile bacterium azoles: separating bunch voltage is 25, and impact energy is 35;
(-) enantiomorph of nitrile bacterium azoles: separating bunch voltage is 20, and impact energy is 40;
(+) enantiomorph of RH-7592: separating bunch voltage is 25, and impact energy is 35;
(-) enantiomorph of RH-7592: separating bunch voltage is 20, and impact energy is 35;
(-) enantiomorph of triazolone: separating bunch voltage is 25, and impact energy is 25;
(+) enantiomorph of triazolone: separating bunch voltage is 25, and impact energy is 30.
Said method of from sample, separating triazole type chirality agricultural chemicals enantiomorph also comprises the step of testing sample being carried out pre-treatment; The method of said pre-treatment comprises the steps: to take by weighing the 20g testing sample and disperses the back adding to be added with in advance in the 34mL abstraction pool of 0.5g florisil silica with 2g zeyssatite; With the mixed liquor formed at 1: 1 with volume ratio by methylene chloride and acetone as extraction solvent; The setting extracting pressure is that 1500psi, extraction temperature are 100 ℃, preheat equilibration time 5min, static extracting 5min; Flush volume is that 60% pond volume and purge time 90s extract with said quick abstraction instrument, circulates 1 time; In receiving flask, adding the 5g anhydrous sodium sulfate after extraction finishes dewaters; Changing 100mL over to concentrates in the bottle; With merging after the said extraction solvent wash bottle of 5mL; 35 ℃ of water-baths are revolved and are steamed to doing; Using 1mL is that the mixed liquor of forming at 1: 1 carries out constant volume by acetonitrile and water with volume ratio; After crossing the filter membrane that the aperture is 0.22 μ m, obtain said testing sample.Said testing sample is preferably soil.
The method of triazole type chirality agricultural chemicals enantiomorph content comprises the steps: in the test sample provided by the invention
1) the triazole type chirality agricultural chemicals enantiomorph standard items mixing with concentration known separates according to the aforementioned method that provides, and writes down the corresponding peak area of every kind of enantiomorph; Concentration value with every kind of enantiomorph is an independent variable, is dependent variable with its corresponding peak area, obtains the one-variable linear regression equation;
2) testing sample is separated according to the aforementioned method that provides, and write down the corresponding peak area of every kind of enantiomorph;
3), obtain the concentration of enantiomorph in the said testing sample with one-variable linear regression equation in the peak area substitution step (1) of every kind of enantiomorph correspondence;
Said triazole type chirality agricultural chemicals is selected from least a in the following compound: own azoles alcohol, Flutriafol, alkene azoles alcohol, Cyproconazole, fluorine ether azoles, fluorine ring azoles, nitrile bacterium azoles, RH-7592 and triazolone;
Said triazole type chirality agricultural chemicals enantiomorph standard items are selected from least a in the following compound: (+) enantiomorph of own azoles alcohol; (-) enantiomorph of own azoles alcohol; (+) enantiomorph of Flutriafol; Flutriafol (-) enantiomorph; (+) enantiomorph of alkene azoles alcohol; (-) enantiomorph of alkene azoles alcohol; Retention time is (+) enantiomorph of 4.35 minutes Cyproconazole; Retention time is (+) enantiomorph of 5.10 minutes Cyproconazole; Retention time is (-) enantiomorph of 5.67 minutes Cyproconazole; Retention time is (-) enantiomorph of 12.51 minutes Cyproconazole; (+) enantiomorph of fluorine ether azoles; (-) enantiomorph of fluorine ether azoles; (+) enantiomorph of fluorine ring azoles; (-) enantiomorph of fluorine ring azoles; (+) enantiomorph of nitrile bacterium azoles; (-) enantiomorph of nitrile bacterium azoles; (+) enantiomorph of RH-7592; (-) enantiomorph of RH-7592; (+) enantiomorph of triazolone and (-) enantiomorph of triazolone.
In the said method, the one-variable linear regression equation of said various enantiomorphs is following:
(+) enantiomorph of own azoles alcohol: y=541x+1700, the independent variable concentration range is 25～500 μ g/L;
(-) enantiomorph of own azoles alcohol: y=526x+1680, the independent variable concentration range is 25～500 μ g/L;
(+) enantiomorph of Flutriafol: y=844x-38.4, the independent variable concentration range is 25～500 μ g/L;
Flutriafol (-) enantiomorph: y=725x-1210, the independent variable concentration range is 25～500 μ g/L;
(+) enantiomorph of alkene azoles alcohol: y=292x+1630, the independent variable concentration range is 25～500 μ g/L;
(-) enantiomorph of alkene azoles alcohol: y=274x+253, the independent variable concentration range is 25～500 μ g/L;
Retention time is (+) enantiomorph of 4.35 minutes Cyproconazole: y=965x+378, and the independent variable concentration range is 9～180;
Retention time is (+) enantiomorph of 5.10 minutes Cyproconazole: y=951x+571, and the independent variable concentration range is 16～320;
Retention time is (-) enantiomorph of 5.67 minutes Cyproconazole: y=930x+259, and the independent variable concentration range is 9～180;
Retention time is (-) enantiomorph of 12.51 minutes Cyproconazole: y=725x+877, and the independent variable concentration range is 16～320;
(+) enantiomorph of fluorine ether azoles: y=344x+2710, the independent variable concentration range is 25～500;
(-) enantiomorph of fluorine ether azoles: y=395x+414, the independent variable concentration range is 25～500;
(+) enantiomorph of fluorine ring azoles: y=694x+1700, the independent variable concentration range is 25～500;
(-) enantiomorph of fluorine ring azoles: y=724x+2280, the independent variable concentration range is 25～500;
(+) enantiomorph of nitrile bacterium azoles: y=337x+1590, the independent variable concentration range is 25～500;
(-) enantiomorph of nitrile bacterium azoles: y=353x+264, the independent variable concentration range is 25～500;
(+) enantiomorph of RH-7592: y=215x-857, the independent variable concentration range is 25～500;
(-) enantiomorph of RH-7592: y=199x+400, the independent variable concentration range is 25～500;
(+) enantiomorph of triazolone: y=318x+2570, the independent variable concentration range is 25～500;
(-) enantiomorph of triazolone: y=319x+1830, the independent variable concentration range is 25～500.
The method of triazole type chirality agricultural chemicals enantiomorph content also comprises the step of testing sample being carried out pre-treatment in the said test sample; The method of said pre-treatment comprises the steps: to take by weighing the 20g testing sample and disperses the back adding to be added with in advance in the 34mL abstraction pool of 0.5g florisil silica with 2g zeyssatite; With the mixed liquor formed at 1: 1 with volume ratio by methylene chloride and acetone as extraction solvent; The setting extracting pressure is that 1500psi, extraction temperature are 100 ℃, preheat equilibration time 5min, static extracting 5min; Flush volume is that 60% pond volume and purge time 90s extract with said quick abstraction instrument, circulates 1 time; In receiving flask, adding the 5g anhydrous sodium sulfate after extraction finishes dewaters; Changing 100mL over to concentrates in the bottle; With merging after the said extraction solvent wash bottle of 5mL; 35 ℃ of water-baths are revolved and are steamed to doing; Using 1mL is that the mixed liquor of forming at 1: 1 carries out constant volume by acetonitrile and water with volume ratio; After crossing the filter membrane that the aperture is 0.22 μ m, obtain said testing sample.Said testing sample is preferably soil.
The characteristic separation method of triazole type chirality agricultural chemicals enantiomorph provided by the invention; Comprise the steps: with loading cellulose-3; The Phenomenex Lux Cellulose-1 chromatographic column of 5-3,5-dimethylphenyl carbamate chirality stationary phase is carried out liquid chromatography in own azoles alcohol, Flutriafol, alkene azoles alcohol, Cyproconazole, fluorine ether azoles, fluorine ring azoles, nitrile bacterium azoles, RH-7592 and the triazolone any one and is separated
Wherein, In the liquid chromatography separating step of own azoles alcohol; Moving phase is for being the mixed liquor formed of 60: 40 acetonitrile and water by volume ratio or being the mixed liquor that 70: 30 first alcohol and water is formed by volume ratio that it is pure that the eluting order of the pure enantiomorph of own azoles is followed successively by the pure and mild left-handed own azoles of the own azoles of dextrorotation;
In the liquid chromatography separating step of Flutriafol; Moving phase is for being that the mixed liquor formed of 50: 50 acetonitrile and water or moving phase are to be the mixed liquor that 70: 30 first alcohol and water is formed by volume ratio by volume ratio, and the eluting order of Flutriafol enantiomorph is followed successively by left-handed Flutriafol and dextrorotation Flutriafol;
In the liquid chromatography separating step of alkene azoles alcohol; Moving phase is for being the mixed liquor formed of 60: 40 acetonitrile and water or moving phase by volume ratio for being the mixed liquor that 75: 25 first alcohol and water is formed by volume ratio, and it is pure that the eluting order of the pure enantiomorph of alkene azoles is followed successively by the pure and mild d-limonene azoles of left-handed alkene azoles;
In the liquid chromatography separating step of Cyproconazole; Moving phase is for being the mixed liquor that 60: 40 acetonitrile and water is formed by volume ratio, and the eluting order of 4 enantiomorphs of Cyproconazole is followed successively by dextrorotation Cyproconazole, dextrorotation Cyproconazole, left-handed Cyproconazole and left-handed Cyproconazole; Or moving phase is for being the mixed liquor that 70: 30 first alcohol and water is formed by volume ratio, and the eluting order of Cyproconazole enantiomorph is followed successively by dextrorotation Cyproconazole, left-handed Cyproconazole, dextrorotation Cyproconazole and left-handed Cyproconazole;
In the liquid chromatography separating step of fluorine ether azoles, moving phase is for being the mixed liquor that 80: 20 acetonitrile and water is formed by volume ratio, and the eluting order of fluorine ether azoles enantiomorph is followed successively by dextrorotation fluorine ether azoles and left-handed fluorine ether azoles;
In the liquid chromatography separating step of fluorine ring azoles; Moving phase is for being that the mixed liquor formed of 90: 10 acetonitrile and water or moving phase are to be the mixed liquor that 90: 10 first alcohol and water is formed by volume ratio by volume ratio, and the eluting order of fluorine ring azoles enantiomorph is followed successively by left-handed fluorine ring azoles and dextrorotation fluorine ring azoles;
In the liquid chromatography separating step of nitrile bacterium azoles; Moving phase is for being that the mixed liquor formed of 90: 10 acetonitrile and water or moving phase are to be the mixed liquor that 90: 10 first alcohol and water is formed by volume ratio by volume ratio, and the eluting order of nitrile bacterium azoles enantiomorph is followed successively by dextrorotation nitrile bacterium azoles and left-handed nitrile bacterium azoles;
In the liquid chromatography separating step of RH-7592; Moving phase is for being that the mixed liquor formed of 90: 10 acetonitrile and water or moving phase are to be the mixed liquor that 90: 10 first alcohol and water is formed by volume ratio by volume ratio, and the eluting order of RH-7592 enantiomorph is followed successively by dextrorotation RH-7592 and left-handed RH-7592;
In the liquid chromatography separating step of triazolone; Moving phase is for being that the mixed liquor formed of 50: 50 acetonitrile and water or moving phase are to be the mixed liquor that 75: 25 first alcohol and water is formed by volume ratio by volume ratio, and the eluting order of triazolone enantiomorph is followed successively by left-handed triazolone and dextrorotation triazolone.
In the said method; Said filling cellulose-3; In the Phenomenex Lux Cellulose-1 chromatographic column of 5-3,5-dimethylphenyl carbamate chirality stationary phase; Said cellulose-3; The particle diameter of 5-3,5-dimethylphenyl carbamate chirality fixed phase stuffing is 3 μ m; The length of said Phenomenex Lux Cellulose-1 chromatographic column is 150 millimeters, and internal diameter is 2.0 millimeters.
The structural formula of above-mentioned own azoles alcohol, Flutriafol, alkene azoles alcohol, Cyproconazole, fluorine ether azoles, fluorine ring azoles, nitrile bacterium azoles, RH-7592 and triazolone is as follows:
The present invention adopts reversed-phase liquid chromatography chiral stationary phase method first, has realized the separated in synchronization analysis of own azoles alcohol (1), Flutriafol (2), alkene azoles alcohol (3), Cyproconazole (4), fluorine ether azoles (5), fluorine ring azoles (6), nitrile bacterium azoles (7), RH-7592 (8) and triazolone 9 kinds of triazole type chirality agricultural chemicals enantiomorphs such as (9) in conjunction with series connection level Four bar mass spectrum.This method adopts loads cellulose-3; 3 μ m particle diameter Lux Cellulose-1 chromatographic columns of 5-3,5-dimethylphenyl carbamate chirality stationary phase; Above-mentioned 9 kinds of chirality agricultural chemicals enantiomorphs on reversed-phase liquid chromatography, have been split; Investigated the influence of different mobile phase compositions to splitting; Optimized separation condition, and adopt online optically-active detecting device clear and definite the eluting order of each enantiomorph; Again mass spectrum multiple-reaction monitoring (MRM) parameter of each agricultural chemicals is optimized; With the online laggard one-step optimization of liquid chromatography mass spectrum parameters such as atomization gas, dry gas, electron spray voltage, collision gas; And eluent gradient elution requirement isochromatic spectrum parameter, set up the instrument analytical method of 9 kinds of triazole type chiralitys of separated in synchronization agricultural chemicals enantiomorph; Use above-mentioned enantiomorph analytical approach at last; With methylene chloride/acetone (50/50) as extraction solvent; Adopt quick solvent extraction appearance (ASE) to extract 9 kinds of chirality agricultural chemicals in the soil; Extract through dry, concentrate, go up machine after constant volume and the filtration and measure; Obtain good mensuration result, set up the synchronization detecting method of 9 kinds of chirality agricultural chemicals enantiomorphs in the soil.This method detection limit is low to moderate 0.5～1.0 μ g/kg.
Description of drawings
Fig. 1 is the LC/MS/MS chromatogram of triazole type chirality agricultural chemicals; Wherein, A is that the LC/MS/MS chromatogram of triazole type chirality agricultural chemicals is always schemed, and b-j is followed successively by the LC/MS/MS chromatogram of own azoles alcohol, Flutriafol, alkene azoles alcohol, Cyproconazole, fluorine ether azoles, fluorine ring azoles, nitrile bacterium azoles, RH-7592 and triazolone.
Embodiment
Below in conjunction with specific embodiment the present invention is done further elaboration, but the present invention is not limited to following examples.Said method is conventional method if no special instructions.Said material all can get from open commercial sources if no special instructions.
The characteristic of embodiment 1, triazole type chirality agricultural chemicals enantiomorph is separated
1. the investigation of Chiral Separation condition
Adopting particle diameter is the filling cellulose-3 of 3 μ m; The Phenomenex Lux Cellulose-1 chiral chromatographic column of 5-3,5-dimethylphenyl carbamate chirality stationary phase; With acetonitrile/water and methanol as moving phase at reversed-phase liquid chromatography; Mapping splits to above-mentioned 9 kinds of chirality agricultural chemicals respectively with the flow velocity of 0.3mL/min and the detection wavelength of 220nm; Investigate the acetonitrile/water volume ratio and be respectively 90/10; 80/20; 70/30; 60/40; 50/50 with the methanol volume ratio be respectively 90/10; 85/15; 80/20; 75/25; The influence that enantiomorph was split in 70/30 o'clock, the result sees table 4 and table 5.
Table 4, triazole type chirality agricultural chemicals enantiomorph chromatographic resolution parameter
Table 5, Cyproconazole enantiomorph chromatographic resolution parameter
2, the characteristic of enantiomorph is separated
With being filled with cellulose-3; The Phenomenex Lux Cellulose-1 chromatographic column of 5-3,5-dimethylphenyl carbamate chirality stationary phase is carried out liquid chromatography in own azoles alcohol (1), Flutriafol (2), alkene azoles alcohol (3), Cyproconazole (4), fluorine ether azoles (5), fluorine ring azoles (6), nitrile bacterium azoles (7), RH-7592 (8) and the triazolone (9) any one and is separated; The eluting order of each enantiomorph when difference flows phase composition that the online optically-active detecting device of employing CHIRALYSER-MP type is clear and definite
Used chromatographic column is that particle diameter is the filling cellulose-3 of 3 μ m, the Phenomenex Lux Cellulose-1 chiral chromatographic column of 5-3,5-dimethylphenyl carbamate chirality stationary phase, and length is 150 millimeters, and internal diameter is 2.0 millimeters, and sample size is 10 μ L;
Wherein, In the liquid chromatography separating step of own azoles alcohol; Moving phase is for being the mixed liquor formed of 60: 40 acetonitrile and water by volume ratio or being the mixed liquor that 70: 30 first alcohol and water is formed by volume ratio that it is pure that the eluting order of the pure enantiomorph of own azoles is followed successively by the pure and mild left-handed own azoles of the own azoles of dextrorotation;
In the liquid chromatography separating step of Flutriafol; Moving phase is for being that the mixed liquor formed of 50: 50 acetonitrile and water or moving phase are to be the mixed liquor that 70: 30 first alcohol and water is formed by volume ratio by volume ratio, and the eluting order of Flutriafol enantiomorph is followed successively by left-handed Flutriafol and dextrorotation Flutriafol;
In the liquid chromatography separating step of alkene azoles alcohol; Moving phase is for being the mixed liquor formed of 60: 40 acetonitrile and water or moving phase by volume ratio for being the mixed liquor that 75: 25 first alcohol and water is formed by volume ratio, and it is pure that the eluting order of the pure enantiomorph of alkene azoles is followed successively by the pure and mild d-limonene azoles of left-handed alkene azoles;
In the liquid chromatography separating step of Cyproconazole; Moving phase is for being the mixed liquor that 60: 40 acetonitrile and water is formed by volume ratio, and the eluting order of 4 enantiomorphs of Cyproconazole is followed successively by dextrorotation Cyproconazole, dextrorotation Cyproconazole, left-handed Cyproconazole and left-handed Cyproconazole; Or moving phase is for being the mixed liquor that 70: 30 first alcohol and water is formed by volume ratio, and the eluting order of Cyproconazole enantiomorph is followed successively by dextrorotation Cyproconazole, left-handed Cyproconazole, dextrorotation Cyproconazole and left-handed Cyproconazole;
In the liquid chromatography separating step of fluorine ether azoles, moving phase is for being the mixed liquor that 80: 20 acetonitrile and water is formed by volume ratio, and the eluting order of fluorine ether azoles enantiomorph is followed successively by dextrorotation fluorine ether azoles and left-handed fluorine ether azoles;
In the liquid chromatography separating step of fluorine ring azoles; Moving phase is for being that the mixed liquor formed of 90: 10 acetonitrile and water or moving phase are to be the mixed liquor that 90: 10 first alcohol and water is formed by volume ratio by volume ratio, and the eluting order of fluorine ring azoles enantiomorph is followed successively by left-handed fluorine ring azoles and dextrorotation fluorine ring azoles;
In the liquid chromatography separating step of nitrile bacterium azoles; Moving phase is for being that the mixed liquor formed of 90: 10 acetonitrile and water or moving phase are to be the mixed liquor that 90: 10 first alcohol and water is formed by volume ratio by volume ratio, and the eluting order of nitrile bacterium azoles enantiomorph is followed successively by dextrorotation nitrile bacterium azoles and left-handed nitrile bacterium azoles;
In the liquid chromatography separating step of RH-7592; Moving phase is for being that the mixed liquor formed of 90: 10 acetonitrile and water or moving phase are to be the mixed liquor that 90: 10 first alcohol and water is formed by volume ratio by volume ratio, and the eluting order of RH-7592 enantiomorph is followed successively by dextrorotation RH-7592 and left-handed RH-7592;
In the liquid chromatography separating step of triazolone; Moving phase is for being that the mixed liquor formed of 50: 50 acetonitrile and water or moving phase are to be the mixed liquor that 75: 25 first alcohol and water is formed by volume ratio by volume ratio, and the eluting order of triazolone enantiomorph is followed successively by left-handed triazolone and dextrorotation triazolone.
Above-mentioned liquid chromatography separation condition is also as shown in table 3; Carry out the separation of above-mentioned agricultural chemicals according to this method, the optically-active eluting order of its degree of separation and every kind of agricultural chemicals enantiomorph is also listed in the table 3.
The optically-active eluting order of table 3, triazole type chirality agricultural chemicals enantiomorph title, separation condition and enantiomorph
aThe Flutriafol Chiral Separation is not obvious, can't calculate its degree of separation, but about to revolve the positive and negative optically-active signal of enantiomorph obvious.
bThe degree of separation of adjacent two chromatographic peaks, i.e. Rs in 4 chromatographic peaks of Cyproconazole
12/ RsX/Rs
34In addition, peak 1 is respectively a pair of enantiomorph with peak 3, peak 2 and peak 4 under the acetonitrile/water condition, under the methanol condition, is respectively a pair of enantiomorph because of eluting order changes peak 1 with peak 2, peak 3 and peak 4.
The synchronous mensuration of embodiment 2, triazole type chirality agricultural chemicals enantiomorph content
1. the foundation of enantiomorph separated in synchronization and LC/MS/MS analytical approach
Standard solution with 9 kinds of chirality agricultural chemicals carries out the mass spectrum Parameter Optimization on three grades of quadrupole rod tandem mass spectrometers of API2000 type respectively; Comprise the quantitative and qualitative ion pair of selected multiple-reaction monitoring (MRM), impact energy (CE), separate a bunch voltage (DP) etc., Optimization result is seen table 2.
Table 2, Mass Spectrometer Method condition
Online with liquid chromatography with this understanding; Adopt the constant ratio of acetonitrile/water and the chromatographic separation condition of 9 kinds of chirality agricultural chemicals of gradient elution program optimization enantiomorph respectively; The result finds to adopt the gradient elution separation to compare permanent degree wash-out can obtain better Chiral Separation degree and chromatographic peak profile, optimizes selected elution requirement and sees table 1.
Table 1, triazole type chirality agricultural chemicals enantiomorph gradient elution separable programming table
Simultaneously, further optimize LC/MS/MS detected parameters such as atomization gas, dry gas, collision gas, ionization voltage, confirm that finally electron spray (ESI) ionization source atomization gas is 15psi; Dry gas 55psi, collision gas 3psi, ionization voltage+5500V; Ion source temperature is 400 ℃, sample size 10 μ L.Formed the Synchronization Analysis instrument method of 9 kinds of chirality agricultural chemicals enantiomorphs provided by the invention through the optimization of above-mentioned chromatographic separation condition and The MS detection parameters, the total ion of typical case with this understanding extracts ion pair chromatogram with each agricultural chemicals and sees accompanying drawing 1.
2, the foundation of 9 kinds of chirality agricultural chemicals enantiomorph synchronized analyzing methods in the soil
1) prepare pedotheque to be measured:
Taking by weighing 20g soil disperses the back adding to be added with in advance in the 34mL abstraction pool of 0.5g florisil silica with 2g zeyssatite; With the mixed liquor formed at 1: 1 with volume ratio by methylene chloride and acetone as extraction solvent; The setting extracting pressure is that 1500psi, extraction temperature are 100 ℃, preheat equilibration time 5min, static extracting time 5min; Flush volume is that 60% pond volume and purge time 90s extract with quick abstraction instrument, circulates 1 time; In receiving flask, adding the 5g anhydrous sodium sulfate after extraction finishes dewaters; Changing 100mL over to concentrates in the bottle; With merging after the said extraction solvent wash bottle of 5mL; 35 ℃ of water-baths are revolved and are steamed to doing; Using 1mL is that the mixed liquor of forming at 1: 1 carries out constant volume by acetonitrile and water with volume ratio; After crossing the filter membrane that the aperture is 0.22 μ m, obtain pedotheque to be measured.
2) production standard curve:
The standard items that use are the potpourri of following various enantiomorphs: (+) enantiomorph of own azoles alcohol; (-) enantiomorph of own azoles alcohol; (+) enantiomorph of Flutriafol; Flutriafol (-) enantiomorph; (+) enantiomorph of alkene azoles alcohol; (-) enantiomorph of alkene azoles alcohol; Retention time is (+) enantiomorph of 4.35 minutes Cyproconazole; Retention time is (+) enantiomorph of 5.10 minutes Cyproconazole; Retention time is (-) enantiomorph of 5.67 minutes Cyproconazole; Retention time is (-) enantiomorph of 12.51 minutes Cyproconazole; (+) enantiomorph of fluorine ether azoles; (-) enantiomorph of fluorine ether azoles; (+) enantiomorph of fluorine ring azoles; (-) enantiomorph of fluorine ring azoles; (+) enantiomorph of nitrile bacterium azoles; (-) enantiomorph of nitrile bacterium azoles; (+) enantiomorph of RH-7592; (-) enantiomorph of RH-7592; (+) enantiomorph of triazolone and (-) enantiomorph of triazolone, the concentration of every kind of enantiomorph is all known in the potpourri.Standard items (being potpourri) are carried out liquid chromatography-tandem mass spectrometry detect, separating each enantiomorph, and write down the corresponding peak area of every kind of enantiomorph; Concentration value with every kind of enantiomorph is an independent variable, is dependent variable with its corresponding peak area, obtains the one-variable linear regression equation;
The actual conditions of liquid chromatography detecting method is: chromatographic column is for loading cellulose-3, and the Phenomenex Lux Cellulose-1 chromatographic column of 5-3,5-dimethylphenyl carbamate stationary phase, length are 150 millimeters, and internal diameter is 2.0 millimeters, and sample size is 10 μ L; The elution buffer that uses is the mixed solution of acetonitrile and water, and type of elution is a gradient elution, and elution speed is 0.3mL/min;
Said gradient elution mode is (also as shown in table 1) as follows:
1min rises to the 6min end, and the volume ratio of water and acetonitrile is 50%: 50% in the mixed solution;
7min rises to the 10min end, and the volume ratio of water and acetonitrile is 30%: 70% in the mixed solution;
11min rises to the 18min end, and the volume ratio of water and acetonitrile is 50%: 50% in the mixed solution;
Table 1, liquid phase chromatogram condition
The method of separating each eluting peak according to the mass-to-charge ratio characteristic of eluting peak retention time and parent ion/daughter ion is (also as shown in table 2) as follows:
Retention time is that 5.72 minutes, the mass-to-charge ratio of the parent ion/daughter ion of detection by quantitative are that the mass-to-charge ratio of the parent ion/daughter ion of 314.4/70.0 and qualitative detection is (+) enantiomorph that the eluting peak of 314.4/159.0 is own azoles alcohol;
Retention time is that 6.50 minutes, the mass-to-charge ratio of the parent ion/daughter ion of detection by quantitative are that the mass-to-charge ratio of the parent ion/daughter ion of 314.4/70.0 and qualitative detection is (-) enantiomorph that the eluting peak of 314.4/159.0 is own azoles alcohol;
Retention time is that 3.27 minutes, the mass-to-charge ratio of the parent ion/daughter ion of detection by quantitative are that the mass-to-charge ratio of the parent ion/daughter ion of 302.1/70.0 and qualitative detection is (-) enantiomorph that the eluting peak of 302.1/123.1 is Flutriafol;
Retention time is that 3.47 minutes, the mass-to-charge ratio of the parent ion/daughter ion of detection by quantitative are that the mass-to-charge ratio of the parent ion/daughter ion of 302.1/70.0 and qualitative detection is (+) enantiomorph that the eluting peak of 302.1/123.1 is Flutriafol;
Retention time is that 6.48 minutes, the mass-to-charge ratio of the parent ion/daughter ion of detection by quantitative are that the mass-to-charge ratio of the parent ion/daughter ion of 326.1/70.0 and qualitative detection is (-) enantiomorph that the eluting peak of 326.1/159.0 is alkene azoles alcohol;
Retention time is that 6.97 minutes, the mass-to-charge ratio of the parent ion/daughter ion of detection by quantitative are that the mass-to-charge ratio of the parent ion/daughter ion of 326.1/70.0 and qualitative detection is (-) enantiomorph that the eluting peak of 326.1/159.0 is alkene azoles alcohol;
Retention time is that 4.35 minutes, the mass-to-charge ratio of the parent ion/daughter ion of detection by quantitative are that the mass-to-charge ratio of the parent ion/daughter ion of 292.2/70.0 and qualitative detection is (+) enantiomorph that the eluting peak of 292.2/125.0 is Cyproconazole;
Retention time is that 5.10 minutes, the mass-to-charge ratio of the parent ion/daughter ion of detection by quantitative are that the mass-to-charge ratio of the parent ion/daughter ion of 292.2/70.0 and qualitative detection is (+) enantiomorph that the eluting peak of 292.2/125.0 is Cyproconazole;
Retention time is that 5.67 minutes, the mass-to-charge ratio of the parent ion/daughter ion of detection by quantitative are that the mass-to-charge ratio of the parent ion/daughter ion of 292.2/70.0 and qualitative detection is (-) enantiomorph that the eluting peak of 292.2/125.0 is Cyproconazole;
Retention time is that 12.51 minutes, the mass-to-charge ratio of the parent ion/daughter ion of detection by quantitative are that the mass-to-charge ratio of the parent ion/daughter ion of 292.2/70.0 and qualitative detection is (-) enantiomorph that the eluting peak of 292.2/125.0 is Cyproconazole;
Retention time is that 6.99 minutes, the mass-to-charge ratio of the parent ion/daughter ion of detection by quantitative are that the mass-to-charge ratio of the parent ion/daughter ion of 372.2/159.0 and qualitative detection is (+) enantiomorph that the eluting peak of 372.2/70.0 is fluorine ether azoles;
Retention time is that 8.52 minutes, the mass-to-charge ratio of the parent ion/daughter ion of detection by quantitative are that the mass-to-charge ratio of the parent ion/daughter ion of 372.2/159.0 and qualitative detection is (-) enantiomorph that the eluting peak of 372.2/70.0 is fluorine ether azoles;
Retention time is that 7.14 minutes, the mass-to-charge ratio of the parent ion/daughter ion of detection by quantitative are that the mass-to-charge ratio of the parent ion/daughter ion of 330.3/121.2 and qualitative detection is (-) enantiomorph that the eluting peak of 330.3/123.2 is fluorine ring azoles;
Retention time is that 11.59 minutes, the mass-to-charge ratio of the parent ion/daughter ion of detection by quantitative are that the mass-to-charge ratio of the parent ion/daughter ion of 330.3/121.2 and qualitative detection is (+) enantiomorph that the eluting peak of 330.3/123.2 is fluorine ring azoles;
Retention time is that 6.05 minutes, the mass-to-charge ratio of the parent ion/daughter ion of detection by quantitative are that the mass-to-charge ratio of the parent ion/daughter ion of 289.2/70.0 and qualitative detection is (+) enantiomorph that the eluting peak of 289.2/125.0 is nitrile bacterium azoles;
Retention time is that 7.77 minutes, the mass-to-charge ratio of the parent ion/daughter ion of detection by quantitative are that the mass-to-charge ratio of the parent ion/daughter ion of 289.2/70.0 and qualitative detection is (-) enantiomorph that the eluting peak of 289.2/125.0 is nitrile bacterium azoles;
Retention time is that 10.66 minutes, the mass-to-charge ratio of the parent ion/daughter ion of detection by quantitative are that the mass-to-charge ratio of the parent ion/daughter ion of 337.2/70.0 and qualitative detection is (+) enantiomorph that the eluting peak of 337.2/125.0 is RH-7592;
Retention time is that 11.66 minutes, the mass-to-charge ratio of the parent ion/daughter ion of detection by quantitative are that the mass-to-charge ratio of the parent ion/daughter ion of 337.2/70.0 and qualitative detection is (-) enantiomorph that the eluting peak of 337.2/125.0 is RH-7592;
Retention time is that 5.02 minutes, the mass-to-charge ratio of the parent ion/daughter ion of detection by quantitative are that the mass-to-charge ratio of the parent ion/daughter ion of 294.1/197.1 and qualitative detection is (-) enantiomorph that the eluting peak of 294.1/69.1 is triazolone;
Retention time is that 5.61 minutes, the mass-to-charge ratio of the parent ion/daughter ion of detection by quantitative are that the mass-to-charge ratio of the parent ion/daughter ion of 294.1/197.1 and qualitative detection is (+) enantiomorph that the eluting peak of 294.1/69.1 is triazolone.
The tandem mass spectrum testing conditions is following: electron spray ionisation source atomization gas pressure is 15psi, and dry gas is 55psi, and the collision atmospheric pressure is 3psi, and ionization voltage is+5500V, and ion source temperature is 400 ℃;
Every kind of enantiomorph is corresponding separates a bunch voltage, impact energy (also as shown in table 2) as follows:
(+) enantiomorph of own azoles alcohol: separating bunch voltage is 25, and impact energy is 35;
(-) enantiomorph of own azoles alcohol: separating bunch voltage is 25, and impact energy is 35;
(-) enantiomorph of Flutriafol: separating bunch voltage is 25, and impact energy is 35;
(+) enantiomorph of Flutriafol: separating bunch voltage is 25, and impact energy is 35;
(-) enantiomorph of alkene azoles alcohol: separating bunch voltage is 25, and impact energy is 35;
(+) enantiomorph of alkene azoles alcohol: separating bunch voltage is 25, and impact energy is 35;
(+) enantiomorph of Cyproconazole: separating bunch voltage is 25, and impact energy is 35;
(+) enantiomorph of Cyproconazole: separating bunch voltage is 25, and impact energy is 35;
(-) enantiomorph of Cyproconazole: separating bunch voltage is 25, and impact energy is 35;
(-) enantiomorph of Cyproconazole: separating bunch voltage is 25, and impact energy is 35;
(+) enantiomorph of fluorine ether azoles: separating bunch voltage is 20, and impact energy is 30;
(-) enantiomorph of fluorine ether azoles: separating bunch voltage is 20, and impact energy is 35;
(-) enantiomorph of fluorine ring azoles: separating bunch voltage is 25, and impact energy is 30;
(+) enantiomorph of fluorine ring azoles: separating bunch voltage is 25, and impact energy is 30;
(+) enantiomorph of nitrile bacterium azoles: separating bunch voltage is 25, and impact energy is 35;
(-) enantiomorph of nitrile bacterium azoles: separating bunch voltage is 20, and impact energy is 40;
(+) enantiomorph of RH-7592: separating bunch voltage is 25, and impact energy is 35;
(-) enantiomorph of RH-7592: separating bunch voltage is 20, and impact energy is 35;
(-) enantiomorph of triazolone: separating bunch voltage is 25, and impact energy is 25;
(+) enantiomorph of triazolone: separating bunch voltage is 25, and impact energy is 30.
Table 2, Mass Spectrometer Method condition
The one-variable linear regression equation that obtains is as shown in table 6,
The linear equation of table 6, triazole type chirality agricultural chemicals enantiomorph
3) detect pedotheque to be measured
According to step 2) identical method separates, and only the potpourri standard items replaced to step 1) gained pedotheque to be measured, and writes down the corresponding peak area of every kind of enantiomorph;
4) one-variable linear regression equation peak area substitution step 2 that every kind of enantiomorph is corresponding) obtains the concentration of every kind of enantiomorph in the testing sample, accomplishes triazole type chirality agricultural chemicals enantiomorph Determination on content in the pedotheque to be measured.
3, accuracy, repeatability and the sensitivity of measuring said method synchronously detects
Be accuracy, repeatability and the sensitivity of estimating this synchronous assay method; Take by weighing the blank pedotheque of 20g, add certain density hybrid standard sample respectively, mix the pedotheque that the back forms different interpolation levels; Handle the back by above-mentioned agent, soil treatment method and go up machine mensuration, the result sees table 7.
Table 7, triazole type chirality agricultural chemicals enantiomorph soil add measures the result
Can know by table 7; The enantiomorph of the 9 kinds of triazole type chirality agricultural chemicals interpolation recovery and repeatability are all better in the soil; Method detectability according to 3 times of signal to noise ratio (S/N ratio) gained is low, detects and is limited to 0.5-1.0 μ g/kg, is applicable to the how residual synchronous detection of above-mentioned chirality agricultural chemicals enantiomorph in the ambient soil.
Claims (10)
1. a method of from sample, separating triazole type chirality agricultural chemicals enantiomorph comprises the steps:
Testing sample is carried out liquid chromatography-tandem mass spectrometry to be detected; Mass-to-charge ratio characteristic according to the parent ion/daughter ion of the mass-to-charge ratio of the parent ion/daughter ion of eluting peak retention time and detection by quantitative and qualitative detection is separated each eluting peak, promptly obtains each triazole type chirality agricultural chemicals enantiomorph;
Said triazole type chirality agricultural chemicals is selected from least a in the following compound: own azoles alcohol, Flutriafol, alkene azoles alcohol, Cyproconazole, fluorine ether azoles, fluorine ring azoles, nitrile bacterium azoles, RH-7592 and triazolone; The condition of said liquid chromatographic detection is following: chromatographic column is for loading cellulose-3, the Phenomenex Lux Cellulose-1 chromatographic column of 5-3,5-dimethylphenyl carbamate stationary phase; The elution buffer that uses is the mixed solution of acetonitrile and water, and type of elution is a gradient elution, and elution speed is 0.3mL/min;
Said gradient elution mode is following:
1min rises to the 6min end, and the volume ratio of water and acetonitrile is 50%: 50% in the mixed solution;
7min rises to the 10min end, and the volume ratio of water and acetonitrile is 30%: 70% in the mixed solution;
11min rises to the 18min end, and the volume ratio of water and acetonitrile is 50%: 50% in the mixed solution;
The method that said mass-to-charge ratio characteristic according to eluting peak retention time and parent ion/daughter ion is separated each eluting peak is following:
Retention time is that 5.72 minutes, the mass-to-charge ratio of the parent ion/daughter ion of detection by quantitative are that the mass-to-charge ratio of the parent ion/daughter ion of 314.4/70.0 and qualitative detection is (+) enantiomorph that the eluting peak of 314.4/159.0 is own azoles alcohol;
Retention time is that 6.50 minutes, the mass-to-charge ratio of the parent ion/daughter ion of detection by quantitative are that the mass-to-charge ratio of the parent ion/daughter ion of 314.4/70.0 and qualitative detection is (-) enantiomorph that the eluting peak of 314.4/159.0 is own azoles alcohol;
Retention time is that 3.27 minutes, the mass-to-charge ratio of the parent ion/daughter ion of detection by quantitative are that the mass-to-charge ratio of the parent ion/daughter ion of 302.1/70.0 and qualitative detection is (-) enantiomorph that the eluting peak of 302.1/123.1 is Flutriafol;
Retention time is that 3.47 minutes, the mass-to-charge ratio of the parent ion/daughter ion of detection by quantitative are that the mass-to-charge ratio of the parent ion/daughter ion of 302.1/70.0 and qualitative detection is (+) enantiomorph that the eluting peak of 302.1/123.1 is Flutriafol;
Retention time is that 6.48 minutes, the mass-to-charge ratio of the parent ion/daughter ion of detection by quantitative are that the mass-to-charge ratio of the parent ion/daughter ion of 326.1/70.0 and qualitative detection is (-) enantiomorph that the eluting peak of 326.1/159.0 is alkene azoles alcohol;
Retention time is that 6.97 minutes, the mass-to-charge ratio of the parent ion/daughter ion of detection by quantitative are that the mass-to-charge ratio of the parent ion/daughter ion of 326.1/70.0 and qualitative detection is (-) enantiomorph that the eluting peak of 326.1/159.0 is alkene azoles alcohol;
Retention time is that 4.35 minutes, the mass-to-charge ratio of the parent ion/daughter ion of detection by quantitative are that the mass-to-charge ratio of the parent ion/daughter ion of 292.2/70.0 and qualitative detection is (+) enantiomorph that the eluting peak of 292.2/125.0 is Cyproconazole;
Retention time is that 5.10 minutes, the mass-to-charge ratio of the parent ion/daughter ion of detection by quantitative are that the mass-to-charge ratio of the parent ion/daughter ion of 292.2/70.0 and qualitative detection is (+) enantiomorph that the eluting peak of 292.2/125.0 is Cyproconazole;
Retention time is that 5.67 minutes, the mass-to-charge ratio of the parent ion/daughter ion of detection by quantitative are that the mass-to-charge ratio of the parent ion/daughter ion of 292.2/70.0 and qualitative detection is (-) enantiomorph that the eluting peak of 292.2/125.0 is Cyproconazole;
Retention time is that 12.51 minutes, the mass-to-charge ratio of the parent ion/daughter ion of detection by quantitative are that the mass-to-charge ratio of the parent ion/daughter ion of 292.2/70.0 and qualitative detection is (-) enantiomorph that the eluting peak of 292.2/125.0 is Cyproconazole;
Retention time is that 6.99 minutes, the mass-to-charge ratio of the parent ion/daughter ion of detection by quantitative are that the mass-to-charge ratio of the parent ion/daughter ion of 372.2/159.0 and qualitative detection is (+) enantiomorph that the eluting peak of 372.2/70.0 is fluorine ether azoles;
Retention time is that 8.52 minutes, the mass-to-charge ratio of the parent ion/daughter ion of detection by quantitative are that the mass-to-charge ratio of the parent ion/daughter ion of 372.2/159.0 and qualitative detection is (-) enantiomorph that the eluting peak of 372.2/70.0 is fluorine ether azoles;
Retention time is that 7.14 minutes, the mass-to-charge ratio of the parent ion/daughter ion of detection by quantitative are that the mass-to-charge ratio of the parent ion/daughter ion of 330.3/121.2 and qualitative detection is (-) enantiomorph that the eluting peak of 330.3/123.2 is fluorine ring azoles;
Retention time is that 11.59 minutes, the mass-to-charge ratio of the parent ion/daughter ion of detection by quantitative are that the mass-to-charge ratio of the parent ion/daughter ion of 330.3/121.2 and qualitative detection is (+) enantiomorph that the eluting peak of 330.3/123.2 is fluorine ring azoles;
Retention time is that 6.05 minutes, the mass-to-charge ratio of the parent ion/daughter ion of detection by quantitative are that the mass-to-charge ratio of the parent ion/daughter ion of 289.2/70.0 and qualitative detection is (+) enantiomorph that the eluting peak of 289.2/125.0 is nitrile bacterium azoles;
Retention time is that 7.77 minutes, the mass-to-charge ratio of the parent ion/daughter ion of detection by quantitative are that the mass-to-charge ratio of the parent ion/daughter ion of 289.2/70.0 and qualitative detection is (-) enantiomorph that the eluting peak of 289.2/125.0 is nitrile bacterium azoles;
Retention time is that 10.66 minutes, the mass-to-charge ratio of the parent ion/daughter ion of detection by quantitative are that the mass-to-charge ratio of the parent ion/daughter ion of 337.2/70.0 and qualitative detection is (+) enantiomorph that the eluting peak of 337.2/125.0 is RH-7592;
Retention time is that 11.66 minutes, the mass-to-charge ratio of the parent ion/daughter ion of detection by quantitative are that the mass-to-charge ratio of the parent ion/daughter ion of 337.2/70.0 and qualitative detection is (-) enantiomorph that the eluting peak of 337.2/125.0 is RH-7592;
Retention time is that 5.02 minutes, the mass-to-charge ratio of the parent ion/daughter ion of detection by quantitative are that the mass-to-charge ratio of the parent ion/daughter ion of 294.1/197.1 and qualitative detection is (-) enantiomorph that the eluting peak of 294.1/69.1 is triazolone;
Retention time is that 5.61 minutes, the mass-to-charge ratio of the parent ion/daughter ion of detection by quantitative are that the mass-to-charge ratio of the parent ion/daughter ion of 294.1/197.1 and qualitative detection is (+) enantiomorph that the eluting peak of 294.1/69.1 is triazolone.
2. method according to claim 1 is characterized in that: in the testing conditions of said liquid chromatography, the length of said chromatographic column is 150 millimeters, and internal diameter is 2.0 millimeters; Sample size is 10 μ L; Said cellulose-3, the particle diameter of 5-3,5-dimethylphenyl carbamate are 3 μ m.
3. method according to claim 1 and 2 is characterized in that: in the said Mass Spectrometer Method condition, electron spray ionisation source atomization gas pressure is 15psi; Dry gas is 55psi; The collision atmospheric pressure is 3psi, and ionization voltage is+5500V, and ion source temperature is 400 ℃;
Every kind of enantiomorph is corresponding separates a bunch voltage, impact energy is following:
(+) enantiomorph of own azoles alcohol: separating bunch voltage is 25, and impact energy is 35;
(-) enantiomorph of own azoles alcohol: separating bunch voltage is 25, and impact energy is 35;
(-) enantiomorph of Flutriafol: separating bunch voltage is 25, and impact energy is 35;
(+) enantiomorph of Flutriafol: separating bunch voltage is 25, and impact energy is 35;
(-) enantiomorph of alkene azoles alcohol: separating bunch voltage is 25, and impact energy is 35;
(+) enantiomorph of alkene azoles alcohol: separating bunch voltage is 25, and impact energy is 35;
(+) enantiomorph of Cyproconazole: separating bunch voltage is 25, and impact energy is 35;
(+) enantiomorph of Cyproconazole: separating bunch voltage is 25, and impact energy is 35;
(-) enantiomorph of Cyproconazole: separating bunch voltage is 25, and impact energy is 35;
(-) enantiomorph of Cyproconazole: separating bunch voltage is 25, and impact energy is 35;
(+) enantiomorph of fluorine ether azoles: separating bunch voltage is 20, and impact energy is 30;
(-) enantiomorph of fluorine ether azoles: separating bunch voltage is 20, and impact energy is 35;
(-) enantiomorph of fluorine ring azoles: separating bunch voltage is 25, and impact energy is 30;
(+) enantiomorph of fluorine ring azoles: separating bunch voltage is 25, and impact energy is 30;
(+) enantiomorph of nitrile bacterium azoles: separating bunch voltage is 25, and impact energy is 35;
(-) enantiomorph of nitrile bacterium azoles: separating bunch voltage is 20, and impact energy is 40;
(+) enantiomorph of RH-7592: separating bunch voltage is 25, and impact energy is 35;
(-) enantiomorph of RH-7592: separating bunch voltage is 20, and impact energy is 35;
(-) enantiomorph of triazolone: separating bunch voltage is 25, and impact energy is 25;
(+) enantiomorph of triazolone: separating bunch voltage is 25, and impact energy is 30.
4. according to the arbitrary described method of claim 1-3, it is characterized in that: said method of from sample, separating triazole type chirality agricultural chemicals enantiomorph also comprises the step of testing sample being carried out pre-treatment;
The method of said pre-treatment comprises the steps: to take by weighing the 20g testing sample and disperses the back adding to be added with in advance in the 34mL abstraction pool of 0.5g florisil silica with 2g zeyssatite; With the mixed liquor formed at 1: 1 with volume ratio by methylene chloride and acetone as extraction solvent; The setting extracting pressure is that 1500psi, extraction temperature are 100 ℃, preheat equilibration time 5min, static extracting 5min; Flush volume is that 60% pond volume and purge time 90s extract with said quick abstraction instrument, circulates 1 time; In receiving flask, adding the 5g anhydrous sodium sulfate after extraction finishes dewaters; Changing 100mL over to concentrates in the bottle; With merging after the said extraction solvent wash bottle of 5mL; 35 ℃ of water-baths are revolved and are steamed to doing; Using 1mL is that the mixed liquor of forming at 1: 1 carries out constant volume by acetonitrile and water with volume ratio; After crossing the filter membrane that the aperture is 0.22 μ m, obtain said testing sample.
5. according to the arbitrary described method of claim 1-4, it is characterized in that: said testing sample is a soil.
6. the method for triazole type chirality agricultural chemicals enantiomorph content in the test sample comprises the steps:
1) the triazole type chirality agricultural chemicals enantiomorph standard items mixing with concentration known separates according to arbitrary said method among the claim 1-5, and writes down the corresponding peak area of every kind of enantiomorph; Concentration value with every kind of enantiomorph is an independent variable, is dependent variable with its corresponding peak area, obtains the one-variable linear regression equation;
2) testing sample is separated according to arbitrary said method among the claim 1-5, and write down the corresponding peak area of every kind of enantiomorph;
3), obtain the concentration of enantiomorph in the said testing sample with one-variable linear regression equation in the peak area substitution step (1) of every kind of enantiomorph correspondence;
Said triazole type chirality agricultural chemicals is selected from least a in the following compound: own azoles alcohol, Flutriafol, alkene azoles alcohol, Cyproconazole, fluorine ether azoles, fluorine ring azoles, nitrile bacterium azoles, RH-7592 and triazolone; Said triazole type chirality agricultural chemicals enantiomorph standard items are selected from least a in the following compound: (+) enantiomorph of own azoles alcohol; (-) enantiomorph of own azoles alcohol; (+) enantiomorph of Flutriafol; Flutriafol (-) enantiomorph; (+) enantiomorph of alkene azoles alcohol; (-) enantiomorph of alkene azoles alcohol; Retention time is (+) enantiomorph of 4.35 minutes Cyproconazole; Retention time is (+) enantiomorph of 5.10 minutes Cyproconazole; Retention time is (-) enantiomorph of 5.67 minutes Cyproconazole; Retention time is (-) enantiomorph of 12.51 minutes Cyproconazole; (+) enantiomorph of fluorine ether azoles; (-) enantiomorph of fluorine ether azoles; (+) enantiomorph of fluorine ring azoles; (-) enantiomorph of fluorine ring azoles; (+) enantiomorph of nitrile bacterium azoles; (-) enantiomorph of nitrile bacterium azoles; (+) enantiomorph of RH-7592; (-) enantiomorph of RH-7592; (+) enantiomorph of triazolone and (-) enantiomorph of triazolone.
7. method according to claim 6 is characterized in that: the one-variable linear regression equation of said various enantiomorphs is following:
(+) enantiomorph of own azoles alcohol: y=541x+1700, the independent variable concentration range is 25～500 μ g/L;
(-) enantiomorph of own azoles alcohol: y=526x+1680, the independent variable concentration range is 25～500 μ g/L;
(+) enantiomorph of Flutriafol: y=844x-38.4, the independent variable concentration range is 25～500 μ g/L;
Flutriafol (-) enantiomorph: y=725x-1210, the independent variable concentration range is 25～500 μ g/L;
(+) enantiomorph of alkene azoles alcohol: y=292x+1630, the independent variable concentration range is 25～500 μ g/L;
(-) enantiomorph of alkene azoles alcohol: y=274x+253, the independent variable concentration range is 25～500 μ g/L;
Retention time is (+) enantiomorph of 4.35 minutes Cyproconazole: y=965x+378, and the independent variable concentration range is 9～180;
Retention time is (+) enantiomorph of 5.10 minutes Cyproconazole: y=951x+571, and the independent variable concentration range is 16～320;
Retention time is (-) enantiomorph of 5.67 minutes Cyproconazole: y=930x+259, and the independent variable concentration range is 9～180;
Retention time is (-) enantiomorph of 12.51 minutes Cyproconazole: y=725x+877, and the independent variable concentration range is 16～320;
(+) enantiomorph of fluorine ether azoles: y=344x+2710, the independent variable concentration range is 25～500;
(-) enantiomorph of fluorine ether azoles: y=395x+414, the independent variable concentration range is 25～500;
(+) enantiomorph of fluorine ring azoles: y=694x+1700, the independent variable concentration range is 25～500;
(-) enantiomorph of fluorine ring azoles: y=724x+2280, the independent variable concentration range is 25～500;
(+) enantiomorph of nitrile bacterium azoles: y=337x+1590, the independent variable concentration range is 25～500;
(-) enantiomorph of nitrile bacterium azoles: y=353x+264, the independent variable concentration range is 25～500;
(+) enantiomorph of RH-7592: y=215x-857, the independent variable concentration range is 25～500;
(-) enantiomorph of RH-7592: y=199x+400, the independent variable concentration range is 25～500;
(+) enantiomorph of triazolone: y=318x+2570, the independent variable concentration range is 25～500;
(-) enantiomorph of triazolone: y=319x+1830, the independent variable concentration range is 25～500.
8. according to claim 6 or 7 described methods, it is characterized in that: the method for triazole type chirality agricultural chemicals enantiomorph content in the said test sample also comprises the step of testing sample being carried out pre-treatment;
The method of said pre-treatment comprises the steps: to take by weighing the 20g testing sample and disperses the back adding to be added with in advance in the 34mL abstraction pool of 0.5g florisil silica with 2g zeyssatite; With the mixed liquor formed at 1: 1 with volume ratio by methylene chloride and acetone as extraction solvent; The setting extracting pressure is that 1500psi, extraction temperature are 100 ℃, preheat equilibration time 5min, static extracting 5min; Flush volume is that 60% pond volume and purge time 90s extract with said quick abstraction instrument, circulates 1 time; In receiving flask, adding the 5g anhydrous sodium sulfate after extraction finishes dewaters; Changing 100mL over to concentrates in the bottle; With merging after the said extraction solvent wash bottle of 5mL; 35 ℃ of water-baths are revolved and are steamed to doing; Using 1mL is that the mixed liquor of forming at 1: 1 carries out constant volume by acetonitrile and water with volume ratio; After crossing the filter membrane that the aperture is 0.22 μ m, obtain said testing sample; Said testing sample is preferably soil.
9. the characteristic separation method of a triazole type chirality agricultural chemicals enantiomorph; Comprise the steps: with loading cellulose-3; The Phenomenex Lux Cellulose-1 chromatographic column of 5-3,5-dimethylphenyl carbamate chirality stationary phase is carried out liquid chromatography in own azoles alcohol, Flutriafol, alkene azoles alcohol, Cyproconazole, fluorine ether azoles, fluorine ring azoles, nitrile bacterium azoles, RH-7592 and the triazolone any one and is separated
Wherein, In the liquid chromatography separating step of own azoles alcohol; Moving phase is for being the mixed liquor formed of 60: 40 acetonitrile and water by volume ratio or being the mixed liquor that 70: 30 first alcohol and water is formed by volume ratio that it is pure that the eluting order of the pure enantiomorph of own azoles is followed successively by the pure and mild left-handed own azoles of the own azoles of dextrorotation;
In the liquid chromatography separating step of Flutriafol; Moving phase is for being that the mixed liquor formed of 50: 50 acetonitrile and water or moving phase are to be the mixed liquor that 70: 30 first alcohol and water is formed by volume ratio by volume ratio, and the eluting order of Flutriafol enantiomorph is followed successively by left-handed Flutriafol and dextrorotation Flutriafol;
In the liquid chromatography separating step of alkene azoles alcohol; Moving phase is for being the mixed liquor formed of 60: 40 acetonitrile and water or moving phase by volume ratio for being the mixed liquor that 75: 25 first alcohol and water is formed by volume ratio, and it is pure that the eluting order of the pure enantiomorph of alkene azoles is followed successively by the pure and mild d-limonene azoles of left-handed alkene azoles;
In the liquid chromatography separating step of Cyproconazole; Moving phase is for being the mixed liquor that 60: 40 acetonitrile and water is formed by volume ratio, and the eluting order of 4 enantiomorphs of Cyproconazole is followed successively by dextrorotation Cyproconazole, dextrorotation Cyproconazole, left-handed Cyproconazole and left-handed Cyproconazole; Or moving phase is for being the mixed liquor that 70: 30 first alcohol and water is formed by volume ratio, and the eluting order of Cyproconazole enantiomorph is followed successively by dextrorotation Cyproconazole, left-handed Cyproconazole, dextrorotation Cyproconazole and left-handed Cyproconazole;
In the liquid chromatography separating step of fluorine ether azoles, moving phase is for being the mixed liquor that 80: 20 acetonitrile and water is formed by volume ratio, and the eluting order of fluorine ether azoles enantiomorph is followed successively by dextrorotation fluorine ether azoles and left-handed fluorine ether azoles;
In the liquid chromatography separating step of fluorine ring azoles; Moving phase is for being that the mixed liquor formed of 90: 10 acetonitrile and water or moving phase are to be the mixed liquor that 90: 10 first alcohol and water is formed by volume ratio by volume ratio, and the eluting order of fluorine ring azoles enantiomorph is followed successively by left-handed fluorine ring azoles and dextrorotation fluorine ring azoles;
In the liquid chromatography separating step of nitrile bacterium azoles; Moving phase is for being that the mixed liquor formed of 90: 10 acetonitrile and water or moving phase are to be the mixed liquor that 90: 10 first alcohol and water is formed by volume ratio by volume ratio, and the eluting order of nitrile bacterium azoles enantiomorph is followed successively by dextrorotation nitrile bacterium azoles and left-handed nitrile bacterium azoles;
In the liquid chromatography separating step of RH-7592; Moving phase is for being that the mixed liquor formed of 90: 10 acetonitrile and water or moving phase are to be the mixed liquor that 90: 10 first alcohol and water is formed by volume ratio by volume ratio, and the eluting order of RH-7592 enantiomorph is followed successively by dextrorotation RH-7592 and left-handed RH-7592;
In the liquid chromatography separating step of triazolone; Moving phase is for being that the mixed liquor formed of 50: 50 acetonitrile and water or moving phase are to be the mixed liquor that 75: 25 first alcohol and water is formed by volume ratio by volume ratio, and the eluting order of triazolone enantiomorph is followed successively by left-handed triazolone and dextrorotation triazolone.
10. method according to claim 9; It is characterized in that: said filling cellulose-3; In the Phenomenex Lux Cellulose-1 chromatographic column of 5-3,5-dimethylphenyl carbamate chirality stationary phase; Said cellulose-3; The particle diameter of 5-3,5-dimethylphenyl carbamate chirality fixed phase stuffing is 3 μ m; The length of said Phenomenex Lux Cellulose-1 chromatographic column is 150 millimeters, and internal diameter is 2.0 millimeters.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110148839.6A CN102353740B (en) | 2011-06-03 | 2011-06-03 | Method for synchronous determination of content of triazole chiral pesticide enantiomers |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110148839.6A CN102353740B (en) | 2011-06-03 | 2011-06-03 | Method for synchronous determination of content of triazole chiral pesticide enantiomers |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102353740A true CN102353740A (en) | 2012-02-15 |
| CN102353740B CN102353740B (en) | 2014-07-30 |
Family
ID=45577344
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110148839.6A Active CN102353740B (en) | 2011-06-03 | 2011-06-03 | Method for synchronous determination of content of triazole chiral pesticide enantiomers |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102353740B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104931614A (en) * | 2015-06-04 | 2015-09-23 | 河南省农业科学院农业质量标准与检测技术研究所 | GC-NPD (gas chromatography-nitrogen phosphorus detector) method for cyproconazole residues and application of method |
| CN105136924A (en) * | 2015-08-21 | 2015-12-09 | 河南省农业科学院农业质量标准与检测技术研究所 | Detection method of epoxiconazole residual quantity in wheat |
| CN105259289A (en) * | 2015-11-02 | 2016-01-20 | 南京大学 | Recognition method of toxic chiral monomers in triazole fungicide waste water |
| CN107102076A (en) * | 2017-04-20 | 2017-08-29 | 西安科技大学 | A kind of method detected in organism with metamifop optical isomer content in environment |
| US11585790B1 (en) | 2020-07-31 | 2023-02-21 | Pace Analytical Services, LLC | Analytical herbicide detection technology |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101358953A (en) * | 2008-09-18 | 2009-02-04 | 中华人民共和国江苏出入境检验检疫局 | Method for simultaneously detecting multi-kind pesticide residues in bee products |
-
2011
- 2011-06-03 CN CN201110148839.6A patent/CN102353740B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101358953A (en) * | 2008-09-18 | 2009-02-04 | 中华人民共和国江苏出入境检验检疫局 | Method for simultaneously detecting multi-kind pesticide residues in bee products |
Non-Patent Citations (11)
| Title |
|---|
| 《Anal Bioanal Chem》 20051103 Garrido Frenich A. et al， Determination of multiclass pesticides in food commodities By pressurized liquid extraction using GC-MS/MS and LC-MS/MS 1106-1118 4-8 第383卷, 第11期 * |
| 《Chirality》 20110419 Qiu Jing et al， Enantiomeric Separation of Triazole Fungicides with 3-�m and 5-�m Particle Chiral Columns by Reverse -Phase High-Performance 479-486 1-8 第23卷, 第6期 * |
| 《Chirality》 20110419 Qiu Jing et al， Enantiomeric Separation of Triazole Fungicides with 3-�m and 5-�m Particle Chiral Columns by Reverse -Phase High-Performance 479-486 9-10 第23卷, 第6期 * |
| FROST S. P. ET AL，: "Extraction of Hexaconazole From Weathered Soils:a Comparison Between Soxhlet Extraction, Microwave-assisted Extraction, Supercritical Fluid Extraction and Accelerated Solvent Extraction", 《ANALYST》, vol. 122, 30 September 1997 (1997-09-30), pages 895 - 898 * |
| GARRIDO FRENICH A. ET AL，: "Determination of multiclass pesticides in food commodities By pressurized liquid extraction using GC–MS/MS and LC–MS/MS", 《ANAL BIOANAL CHEM》, vol. 383, no. 11, 3 November 2005 (2005-11-03), pages 1106 - 1118 * |
| QIN TIAN ET AL，: "Enantiomeric separation of chiral pesticides by high Performance liquid chromatography on cellulose tris-3,5-dimethyl carbamate stationary phase under reversed phase conditions", 《JOURNAL OF SEPARATION SCIENCE》, vol. 30, no. 3, 13 February 2007 (2007-02-13), pages 310 - 321 * |
| QIU JING ET AL，: "Enantiomeric Separation of Triazole Fungicides with 3-µm and 5-µm Particle Chiral Columns by Reverse -Phase High-Performance", 《CHIRALITY》, vol. 23, no. 6, 19 April 2011 (2011-04-19), pages 479 - 486 * |
| 王新全 等，: "三唑醇对映体的反相高效液相色谱拆分热力学研究", 《农药学学报》, vol. 13, no. 1, 31 January 2011 (2011-01-31), pages 53 - 58 * |
| 王鹏 等，: "《第九届全国农药质量管理与分析技术交流会论文集》", 13 November 2008, article "手性农药及对映体分析", pages: 94-103 * |
| 田芹 等，: "反相色谱条件下三唑类手性农药对映异构体的拆分", 《分析化学研究简报》, vol. 38, no. 5, 31 May 2010 (2010-05-31), pages 688 - 692 * |
| 程莉: "《中国优秀硕士学位论文全文数据库农业科技辑》", 31 May 2011, article "手性农药腈菌唑和茚虫威在蔬菜水果中的残留分析方法研究", pages: 16-46 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104931614A (en) * | 2015-06-04 | 2015-09-23 | 河南省农业科学院农业质量标准与检测技术研究所 | GC-NPD (gas chromatography-nitrogen phosphorus detector) method for cyproconazole residues and application of method |
| CN105136924A (en) * | 2015-08-21 | 2015-12-09 | 河南省农业科学院农业质量标准与检测技术研究所 | Detection method of epoxiconazole residual quantity in wheat |
| CN105259289A (en) * | 2015-11-02 | 2016-01-20 | 南京大学 | Recognition method of toxic chiral monomers in triazole fungicide waste water |
| CN105259289B (en) * | 2015-11-02 | 2017-05-17 | 南京大学 | Recognition method of toxic chiral monomers in triazole fungicide waste water |
| CN107102076A (en) * | 2017-04-20 | 2017-08-29 | 西安科技大学 | A kind of method detected in organism with metamifop optical isomer content in environment |
| CN107102076B (en) * | 2017-04-20 | 2020-06-05 | 西安科技大学 | Method for detecting content of metamifop optical isomer in organism and environment |
| US11585790B1 (en) | 2020-07-31 | 2023-02-21 | Pace Analytical Services, LLC | Analytical herbicide detection technology |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102353740B (en) | 2014-07-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Li et al. | Simultaneous enantioselective determination of triazole fungicides in soil and water by chiral liquid chromatography/tandem mass spectrometry | |
| Fux et al. | Development of an ultra-performance liquid chromatography–mass spectrometry method for the detection of lipophilic marine toxins | |
| Li et al. | Simultaneous enantioselective determination of fenbuconazole and its main metabolites in soil and water by chiral liquid chromatography/tandem mass spectrometry | |
| CN102353740B (en) | Method for synchronous determination of content of triazole chiral pesticide enantiomers | |
| CN107247105B (en) | A kind of method that Solid Phase Extraction-high performance liquid chromatography-tandem mass method detects perchlorate in tealeaves | |
| CN107664670B (en) | The remaining ultra performance liquid chromatography of kind bacterium azoles-tandem mass spectrum detection method in corn | |
| CN108072727A (en) | Method that is a kind of while measuring 23 kinds of organic chlorine agriculture chemicals residual quantities in Radix Notoginseng | |
| Zhang et al. | Rapid gas chromatography with flame photometric detection of multiple organophosphorus pesticides in Salvia miltiorrhizae after ultrasonication assisted one-step extraction | |
| Chen et al. | Study of the ESI and APCI interfaces for the UPLC–MS/MS analysis of pesticides in traditional Chinese herbal medicine | |
| Wang et al. | Simultaneous determination of six plant growth regulators in fruits using high performance liquid chromatography based on solid-phase extraction and cleanup with a novel mixed-mode functionalized calixarene sorbent | |
| Jones et al. | Investigating sub-2 μm particle stationary phase supercritical fluid chromatography coupled to mass spectrometry for chemical profiling of chamomile extracts | |
| De Gerónimo et al. | A simple and rapid analytical methodology based on liquid chromatography-tandem mass spectrometry for monitoring pesticide residues in soils from Argentina | |
| CN105758946A (en) | Method for determining residual quantity of 15 kinds of triazole type pesticides in fruit | |
| CN107727760A (en) | A kind of assay method of Pesticides in Tea medicine enantiomter residual quantity | |
| Qi et al. | Use of liquid chromatography-quadrupole time-of-flight mass spectrometry for enantioselective separation and determination of pyrisoxazole in vegetables, strawberry and soil | |
| Chen et al. | Determination of four major saponins in the seeds of Aesculus chinensis Bunge using accelerated solvent extraction followed by high-performance liquid chromatography and electrospray-time of flight mass spectrometry | |
| CN105954422A (en) | Method for quick detection of content of citrinin in traditional Chinese medicinal materials | |
| Yang et al. | A green and effective method for the determination of metalaxyl enantiomers in tobacco and soil by supercritical fluid chromatography–tandem mass spectrometry | |
| CN105548431A (en) | Method for simultaneously detecting residual quantities of oxamyl and oxamyl oxime in vegetable/fruits | |
| CN110441453B (en) | Method for separating and detecting phosphamidon isomers | |
| Yang et al. | Determination of chlorinated phenoxy acid herbicides in tobacco by modified QuEChERS extraction and high-performance liquid chromatography/tandem mass spectrometry | |
| CN108508130B (en) | Method for splitting and measuring enantiomers of chiral pesticides metalaxyl and dimethomorph by ultra-high performance combined chromatography-tandem mass spectrometry technology | |
| Kanda et al. | Rapid determination of nitroimidazole residues in honey by liquid chromatography/tandem mass spectrometry | |
| CN109030665A (en) | The detection method of beet alkali content in hydrophilic liquid phase chromatographic tandem mass spectrometric determination red beet | |
| Martínez et al. | Determination of pyrethroid insecticides in vegetables with liquid chromatography using detection by electrospray mass spectrometry |
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 |