CN102353740B - 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
- CN102353740B CN102353740B CN201110148839.6A CN201110148839A CN102353740B CN 102353740 B CN102353740 B CN 102353740B CN 201110148839 A CN201110148839 A CN 201110148839A CN 102353740 B CN102353740 B CN 102353740B
- Authority
- CN
- China
- Prior art keywords
- enantiomorph
- mass
- ion
- charge ratio
- azoles
- 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 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 the Detection Technologies of Pesticide Residues field, relate to a kind of method of synchronous determination of content of triazole chiral pesticide enantiomers.
Background technology
May there is huge difference in all many-sides such as activity, toxicity, absorption, degraded, metabolism and elimination of chiral pesticide enantiomers in physical environment and biosome, the biologically active showing such as two enantiomorphs is different often, or even diametrically opposite: an enantiomorph has good preventive and therapeutic effect to disease and pest, another enantiomorph activity is very micro-, or without effect, even may produce stronger toxic and side effect.Be subject to the impact of the market demand, economic benefit and environmental protection factor; the content that people also start to adopt single-activity enantiomorph or improve certain active enantiomorph; improve prevention and control of plant diseases, pest control effect and obtain higher economic benefit, alleviating the pollution of agricultural chemicals to environment simultaneously.Therefore, the research that is to the compartment analysis of chiral pesticide enantiomers and selective row becomes new focus, and correlative study progressively increases and deepens continuously.
Triazole pesticide is the chemical pesticide that a large class has chirality feature, between its enantiomorph, demonstrate the diverse living features of character, if the bactericidal activity of R-alkene azoles alcohol is far away higher than S-enantiomorph, and the plant growth regulating activity of S-enantiomorph is than R-mapping height, this phenomenon shows more obviously on uniconazole P.(-)-enantiomorph bactericidal activity of own azoles alcohol and Tebuconazole is all higher than (+)-enantiomorph, and (+)-Flutriafol activity is higher than (-)-Flutriafol.Between two enantiomorphs of triazolone, activity difference is very little, but its reduzate Triadimenol has four enantiomorphs, 1S wherein, and 2R-enantiomorph has higher bactericidal activity.Aspect residual and katabolism in environmental and biological materials, these agricultural chemicals also have larger difference.As epoxiconazole and cyproconazole enantiomorph have stereoselectivity degradation behavior in multiple soil, there is in alkaline soils degradation selectivity in cis epoxiconazole under oxygen consumption condition, also exists the difference of degradation rate between four isomeride of Cyproconazole.Family's rabbit ear vein is injected after own azoles alcohol raceme, increase in time the concentration of (-)-own azoles alcohol in blood plasma and be obviously greater than its enantiomorph concentration, in heart, liver, kidney, spleen and brain tissue, (+)-own azoles alcohol is also eliminated soon than (-)-own azoles alcohol, and the stereoselectivity behavior in liver is the most obvious.
The stereoselectivity behaviors such as the activity of research triazole type chiral pesticide enantiomers, residual, degraded and metabolism, just need to split its enantiomorph, set up effective, sensitive Chiral Separation analytical approach.The method for splitting appearing in the newspapers is at present more, as with chirality OD (cellulose-3,5-3,5-dimethylphenyl carbamate) fixing can resolution triazolone in positive liquid chromatography, the multiple triazole bactericidal agent such as own azoles alcohol, Tebuconazole; With germifuge such as the detachable triazolone of Sulfonated beta-schardinger dextrin-Capillary Electrophoresis, own azoles alcohol and Tebuconazoles.With commercial chirality AD post (amylose-3,5-3,5-dimethylphenyl carbamate) 6 kinds of triazole pesticides such as detachable Tebuconazole, own azoles alcohol under supercritical fluid chromatography condition.In these methods, liquid chromatography Chiral Stationary Phases is the most general and easy to operate, is widely used.But existing liquid chromatography fado adopts normal-phase chromatography and UV-detector to carry out the analysis of enantiomorph, generally can only carry out separation and detection to a kind of enantiomorph of Chiral pesticide.Because UV-detector is a kind of common detector, during working sample, be easily subject to the interference of sample substrate and affect the selectivity of method, the sensitivity of this detecting device is simultaneously also relatively low, separated in synchronization and the high-sensitivity detection that therefore cannot accomplish multiple chiral pesticide enantiomers.
Summary of the invention
A kind of method that the object of this invention is to provide synchronous determination of content of triazole chiral pesticide enantiomers.
Provided by the invention from sample the method for separated triazole type chiral pesticide enantiomers, comprise the steps:
Testing sample is carried out to liquid chromatography-tandem mass spectrometry detection, according to eluting peak retention time and the mass-to-charge ratio of parent ion/daughter ion quantitatively detecting and each eluting peak of mass-to-charge ratio character separation of the parent ion/daughter ion of qualitative detection, obtain each triazole type chiral pesticide enantiomers;
Described triazole type Chiral pesticide is selected from least one in following compound: own azoles alcohol, Flutriafol, alkene azoles alcohol, Cyproconazole, fluorine ether azoles, epoxiconazole, nitrile bacterium azoles, RH-7592 and triazolone;
The condition of described liquid chromatographic detection is as follows: chromatographic column is for loading cellulose-3, and 5-3,5-dimethylphenyl carbamate is the Phenomenex Lux Cellulose-1 chromatographic column of phase fixedly; The mixed solution that the elution buffer using is acetonitrile and water, type of elution is gradient elution, elution speed is 0.3mL/min;
Described gradient elution mode is as follows:
1min rises to 6min end, and in mixed solution, the volume ratio of water and acetonitrile is 50%: 50%;
7min rises to 10min end, and in mixed solution, the volume ratio of water and acetonitrile is 30%: 70%;
11min rises to 18min end, and in mixed solution, the volume ratio of water and acetonitrile is 50%: 50%;
The described method according to each eluting peak of mass-to-charge ratio character separation of eluting peak retention time and parent ion/daughter ion is as follows:
The mass-to-charge ratio of parent ion/daughter ion that retention time is 5.72 minutes, quantitatively detect is (+) enantiomorph that eluting peak that the mass-to-charge ratio of the parent ion/daughter ion of 314.4/70.0 and qualitative detection is 314.4/159.0 is own azoles alcohol;
The mass-to-charge ratio of parent ion/daughter ion that retention time is 6.50 minutes, quantitatively detect is (-) enantiomorph that eluting peak that the mass-to-charge ratio of the parent ion/daughter ion of 314.4/70.0 and qualitative detection is 314.4/159.0 is own azoles alcohol;
The mass-to-charge ratio of parent ion/daughter ion that retention time is 3.27 minutes, quantitatively detect is (-) enantiomorph that eluting peak that the mass-to-charge ratio of the parent ion/daughter ion of 302.1/70.0 and qualitative detection is 302.1/123.1 is Flutriafol;
The mass-to-charge ratio of parent ion/daughter ion that retention time is 3.47 minutes, quantitatively detect is (+) enantiomorph that eluting peak that the mass-to-charge ratio of the parent ion/daughter ion of 302.1/70.0 and qualitative detection is 302.1/123.1 is Flutriafol;
The mass-to-charge ratio of parent ion/daughter ion that retention time is 6.48 minutes, quantitatively detect is (-) enantiomorph that eluting peak that the mass-to-charge ratio of the parent ion/daughter ion of 326.1/70.0 and qualitative detection is 326.1/159.0 is alkene azoles alcohol;
The mass-to-charge ratio of parent ion/daughter ion that retention time is 6.97 minutes, quantitatively detect is (-) enantiomorph that eluting peak that the mass-to-charge ratio of the parent ion/daughter ion of 326.1/70.0 and qualitative detection is 326.1/159.0 is alkene azoles alcohol;
The mass-to-charge ratio of parent ion/daughter ion that retention time is 4.35 minutes, quantitatively detect is (+) enantiomorph that eluting peak that the mass-to-charge ratio of the parent ion/daughter ion of 292.2/70.0 and qualitative detection is 292.2/125.0 is Cyproconazole;
The mass-to-charge ratio of parent ion/daughter ion that retention time is 5.10 minutes, quantitatively detect is (+) enantiomorph that eluting peak that the mass-to-charge ratio of the parent ion/daughter ion of 292.2/70.0 and qualitative detection is 292.2/125.0 is Cyproconazole;
The mass-to-charge ratio of parent ion/daughter ion that retention time is 5.67 minutes, quantitatively detect is (-) enantiomorph that eluting peak that the mass-to-charge ratio of the parent ion/daughter ion of 292.2/70.0 and qualitative detection is 292.2/125.0 is Cyproconazole;
The mass-to-charge ratio of parent ion/daughter ion that retention time is 12.51 minutes, quantitatively detect is (-) enantiomorph that eluting peak that the mass-to-charge ratio of the parent ion/daughter ion of 292.2/70.0 and qualitative detection is 292.2/125.0 is Cyproconazole;
The mass-to-charge ratio of parent ion/daughter ion that retention time is 6.99 minutes, quantitatively detect is (+) enantiomorph that eluting peak that the mass-to-charge ratio of the parent ion/daughter ion of 372.2/159.0 and qualitative detection is 372.2/70.0 is fluorine ether azoles;
The mass-to-charge ratio of parent ion/daughter ion that retention time is 8.52 minutes, quantitatively detect is (-) enantiomorph that eluting peak that the mass-to-charge ratio of the parent ion/daughter ion of 372.2/159.0 and qualitative detection is 372.2/70.0 is fluorine ether azoles;
The mass-to-charge ratio of parent ion/daughter ion that retention time is 7.14 minutes, quantitatively detect is (-) enantiomorph that eluting peak that the mass-to-charge ratio of the parent ion/daughter ion of 330.3/121.2 and qualitative detection is 330.3/123.2 is epoxiconazole;
The mass-to-charge ratio of parent ion/daughter ion that retention time is 11.59 minutes, quantitatively detect is (+) enantiomorph that eluting peak that the mass-to-charge ratio of the parent ion/daughter ion of 330.3/121.2 and qualitative detection is 330.3/123.2 is epoxiconazole;
The mass-to-charge ratio of parent ion/daughter ion that retention time is 6.05 minutes, quantitatively detect is (+) enantiomorph that eluting peak that the mass-to-charge ratio of the parent ion/daughter ion of 289.2/70.0 and qualitative detection is 289.2/125.0 is nitrile bacterium azoles;
The mass-to-charge ratio of parent ion/daughter ion that retention time is 7.77 minutes, quantitatively detect is (-) enantiomorph that eluting peak that the mass-to-charge ratio of the parent ion/daughter ion of 289.2/70.0 and qualitative detection is 289.2/125.0 is nitrile bacterium azoles;
The mass-to-charge ratio of parent ion/daughter ion that retention time is 10.66 minutes, quantitatively detect is (+) enantiomorph that eluting peak that the mass-to-charge ratio of the parent ion/daughter ion of 337.2/70.0 and qualitative detection is 337.2/125.0 is RH-7592;
The mass-to-charge ratio of parent ion/daughter ion that retention time is 11.66 minutes, quantitatively detect is (-) enantiomorph that eluting peak that the mass-to-charge ratio of the parent ion/daughter ion of 337.2/70.0 and qualitative detection is 337.2/125.0 is RH-7592;
The mass-to-charge ratio of parent ion/daughter ion that retention time is 5.02 minutes, quantitatively detect is (-) enantiomorph that eluting peak that the mass-to-charge ratio of the parent ion/daughter ion of 294.1/197.1 and qualitative detection is 294.1/69.1 is triazolone;
The mass-to-charge ratio of parent ion/daughter ion that retention time is 5.61 minutes, quantitatively detect is (+) enantiomorph that eluting peak that the mass-to-charge ratio of the parent ion/daughter ion of 294.1/197.1 and qualitative detection is 294.1/69.1 is triazolone.
Described in said method, in the testing conditions of liquid chromatography, the length of described chromatographic column is 150 millimeters, and internal diameter is 2.0 millimeters; Sample size is 10 μ L; Described cellulose-3, the particle diameter of 5-3,5-dimethylphenyl carbamate is 3 μ m.
In described Mass Spectrometer Method condition, electron spray ionisation source atomization gas pressure is 15psi, and dry gas is 55psi, and collision atmospheric pressure is 3psi, be+5500V of ionization voltage, and ion source temperature is 400 ℃;
Solution bunch voltage, impact energy that every kind of enantiomorph is corresponding are 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 epoxiconazole: separating bunch voltage is 25, and impact energy is 30;
(+) enantiomorph of epoxiconazole: 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.
Described from sample the method for separated triazole type chiral pesticide enantiomers, also comprise the step of testing sample being carried out to pre-treatment; The method of described pre-treatment comprises the steps: to take after 20g testing sample disperses with 2g zeyssatite and adds in the 34mL abstraction pool that is added with in advance 0.5g florisil silica, to be usingd mixed liquor that volume ratio forms at 1: 1 by methylene chloride and acetone as extraction solvent, 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 described rapid extracting device, circulates 1 time; After extraction, in receiving flask, add 5g anhydrous sodium sulfate to dewater, proceed in the concentrated bottle of 100mL, with merging after extraction solvent wash bottle described in 5mL, 35 ℃ of water-baths are revolved and are steamed to dry, with 1mL, by acetonitrile and water, take the mixed liquor that volume ratio formed as 1: 1 and carry out constant volume, cross after the filter membrane that aperture is 0.22 μ m, obtain described testing sample.Described testing sample is preferably soil.
In detection sample provided by the invention, the method for triazole type chiral pesticide enantiomers content, comprises the steps:
1) the triazole type chiral pesticide enantiomers standard items of concentration known are mixed and carry out separation according to the aforementioned method providing, and record every kind of peak area that enantiomorph is corresponding; The concentration value of every kind of enantiomorph of take is independent variable, and take its corresponding peak area is dependent variable, obtains one-variable linear regression equation;
2) testing sample is carried out to separation according to the aforementioned method providing, and record every kind of peak area that enantiomorph is corresponding;
3), by every kind of middle one-variable linear regression equation of peak area substitution step (1) that enantiomorph is corresponding, obtain the concentration of enantiomorph in described testing sample;
Described triazole type Chiral pesticide is selected from least one in following compound: own azoles alcohol, Flutriafol, alkene azoles alcohol, Cyproconazole, fluorine ether azoles, epoxiconazole, nitrile bacterium azoles, RH-7592 and triazolone;
Described triazole type chiral pesticide enantiomers standard items are selected from least one in 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 the Cyproconazole of 4.35 minutes, retention time is (+) enantiomorph of the Cyproconazole of 5.10 minutes, retention time is (-) enantiomorph of the Cyproconazole of 5.67 minutes, retention time is (-) enantiomorph of the Cyproconazole of 12.51 minutes, (+) enantiomorph of fluorine ether azoles, (-) enantiomorph of fluorine ether azoles, (+) enantiomorph of epoxiconazole, (-) enantiomorph of epoxiconazole, (+) 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 said method, the one-variable linear regression equation of described various enantiomorphs is as follows:
(+) enantiomorph of own azoles alcohol: y=541x+1700, independent variable concentration range is 25～500 μ g/L;
(-) enantiomorph of own azoles alcohol: y=526x+1680, independent variable concentration range is 25～500 μ g/L;
(+) enantiomorph of Flutriafol: y=844x-38.4, independent variable concentration range is 25～500 μ g/L;
Flutriafol (-) enantiomorph: y=725x-1210, independent variable concentration range is 25～500 μ g/L;
(+) enantiomorph of alkene azoles alcohol: y=292x+1630, independent variable concentration range is 25～500 μ g/L;
(-) enantiomorph of alkene azoles alcohol: y=274x+253, independent variable concentration range is 25～500 μ g/L;
Retention time is (+) enantiomorph of the Cyproconazole of 4.35 minutes: y=965x+378, and independent variable concentration range is 9～180;
Retention time is (+) enantiomorph of the Cyproconazole of 5.10 minutes: y=951x+571, and independent variable concentration range is 16～320;
Retention time is (-) enantiomorph of the Cyproconazole of 5.67 minutes: y=930x+259, and independent variable concentration range is 9～180;
Retention time is (-) enantiomorph of the Cyproconazole of 12.51 minutes: y=725x+877, and independent variable concentration range is 16～320;
(+) enantiomorph of fluorine ether azoles: y=344x+2710, independent variable concentration range is 25～500;
(-) enantiomorph of fluorine ether azoles: y=395x+414, independent variable concentration range is 25～500;
(+) enantiomorph of epoxiconazole: y=694x+1700, independent variable concentration range is 25～500;
(-) enantiomorph of epoxiconazole: y=724x+2280, independent variable concentration range is 25～500;
(+) enantiomorph of nitrile bacterium azoles: y=337x+1590, independent variable concentration range is 25～500;
(-) enantiomorph of nitrile bacterium azoles: y=353x+264, independent variable concentration range is 25～500;
(+) enantiomorph of RH-7592: y=215x-857, independent variable concentration range is 25～500;
(-) enantiomorph of RH-7592: y=199x+400, independent variable concentration range is 25～500;
(+) enantiomorph of triazolone: y=318x+2570, independent variable concentration range is 25～500;
(-) enantiomorph of triazolone: y=319x+1830, independent variable concentration range is 25～500.
In described detection sample, the method for triazole type chiral pesticide enantiomers content, also comprises the step of testing sample being carried out to pre-treatment; The method of described pre-treatment comprises the steps: to take after 20g testing sample disperses with 2g zeyssatite and adds in the 34mL abstraction pool that is added with in advance 0.5g florisil silica, to be usingd mixed liquor that volume ratio forms at 1: 1 by methylene chloride and acetone as extraction solvent, 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 described rapid extracting device, circulates 1 time; After extraction, in receiving flask, add 5g anhydrous sodium sulfate to dewater, proceed in the concentrated bottle of 100mL, with merging after extraction solvent wash bottle described in 5mL, 35 ℃ of water-baths are revolved and are steamed to dry, with 1mL, by acetonitrile and water, take the mixed liquor that volume ratio formed as 1: 1 and carry out constant volume, cross after the filter membrane that aperture is 0.22 μ m, obtain described testing sample.Described testing sample is preferably soil.
The character separation method of triazole type chiral pesticide enantiomers provided by the invention, comprise the steps: with loading cellulose-3,5-3,5-dimethylphenyl carbamate chirality fixedly the Phenomenex Lux Cellulose-1 chromatographic column of phase that own azoles alcohol, Flutriafol, alkene azoles alcohol, Cyproconazole, fluorine ether azoles, epoxiconazole, nitrile bacterium azoles, RH-7592 and any one in triazolone are carried out to liquid chromatography is separated
Wherein, in the liquid chromatography separating step of own azoles alcohol, the mixed liquor that the mixed liquor that the acetonitrile that mobile phase is is 60: 40 by volume ratio and water form or the first alcohol and water that is 70: 30 by volume ratio form, the eluting order of own azoles alcohol enantiomorph is followed successively by the own azoles alcohol of dextrorotation and left-handed own azoles alcohol;
In the liquid chromatography separating step of Flutriafol, the mixed liquor that the first alcohol and water that the mixed liquor that the acetonitrile that mobile phase is is 50: 50 by volume ratio and water form or mobile phase are is 70: 30 by volume ratio forms, 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, the mixed liquor that the first alcohol and water that the mixed liquor that the acetonitrile that mobile phase is is 60: 40 by volume ratio and water form or mobile phase are is 75: 25 by volume ratio forms, the eluting order of alkene azoles alcohol enantiomorph is followed successively by left-handed alkene azoles alcohol and d-limonene azoles alcohol;
In the liquid chromatography separating step of Cyproconazole, the mixed liquor that the acetonitrile that mobile phase is is 60: 40 by volume ratio and water form, the eluting order of 4 enantiomorphs of Cyproconazole is followed successively by dextrorotation Cyproconazole, dextrorotation Cyproconazole, left-handed Cyproconazole and left-handed Cyproconazole; Or the mixed liquor that forms for the first alcohol and water that is 70: 30 by volume ratio of mobile phase, 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, the mixed liquor that the acetonitrile that mobile phase is is 80: 20 by volume ratio and water form, 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 epoxiconazole, the mixed liquor that the first alcohol and water that the mixed liquor that the acetonitrile that mobile phase is is 90: 10 by volume ratio and water form or mobile phase are is 90: 10 by volume ratio forms, the eluting order of epoxiconazole enantiomorph is followed successively by left-handed epoxiconazole and dextrorotation epoxiconazole;
In the liquid chromatography separating step of nitrile bacterium azoles, the mixed liquor that the first alcohol and water that the mixed liquor that the acetonitrile that mobile phase is is 90: 10 by volume ratio and water form or mobile phase are is 90: 10 by volume ratio forms, 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, the mixed liquor that the first alcohol and water that the mixed liquor that the acetonitrile that mobile phase is is 90: 10 by volume ratio and water form or mobile phase are is 90: 10 by volume ratio forms, 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, the mixed liquor that the first alcohol and water that the mixed liquor that the acetonitrile that mobile phase is is 50: 50 by volume ratio and water form or mobile phase are is 75: 25 by volume ratio forms, the eluting order of triazolone enantiomorph is followed successively by left-handed triazolone and dextrorotation triazolone.
In said method, described filling cellulose-3,5-3,5-dimethylphenyl carbamate chirality is fixedly in the Phenomenex Lux Cellulose-1 chromatographic column of phase, described cellulose-3, the particle diameter of 5-3,5-dimethylphenyl carbamate chirality fixed phase stuffing is 3 μ m, the length of described 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, epoxiconazole, nitrile bacterium azoles, RH-7592 and triazolone is as follows:
The present invention adopts reversed-phase liquid chromatography Chiral Stationary Phases first, has realized the separated in synchronization analysis of 9 kinds of triazole type chiral pesticide enantiomers such as own azoles alcohol (1), Flutriafol (2), alkene azoles alcohol (3), Cyproconazole (4), fluorine ether azoles (5), epoxiconazole (6), nitrile bacterium azoles (7), RH-7592 (8) and triazolone (9) in conjunction with series connection level Four bar mass spectrum.The method adopts loads cellulose-3,5-3,5-dimethylphenyl carbamate chirality is 3 μ m particle diameter Lux Cellulose-1 chromatographic columns of phase fixedly, above-mentioned 9 kinds of chiral pesticide enantiomers on reversed-phase liquid chromatography, have been split, different mobile phase compositions have been investigated to the impact splitting, optimized separation condition, and adopt online polarimetric detector 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 the 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 chiral pesticide enantiomers of separated in synchronization; Finally use above-mentioned enantiomorph analytical approach, using methylene chloride/acetone (50/50) as extraction solvent, adopt quick solvent extraction instrument (ASE) to extract 9 kinds of Chiral pesticides in soil, machine mensuration go up in extract drying, concentrated, constant volume and filtration afterwards, obtain good measurement result, set up the synchronization detecting method of 9 kinds of chiral pesticide enantiomers in soil.The method detection limit is low to moderate 0.5～1.0 μ g/kg.
Accompanying drawing explanation
Fig. 1 is the LC/MS/MS chromatogram of triazole type Chiral pesticide, wherein, a is that the LC/MS/MS chromatogram of triazole type Chiral pesticide 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, epoxiconazole, nitrile bacterium azoles, RH-7592 and triazolone.
Embodiment
Below in conjunction with specific embodiment, the present invention is further elaborated, but the present invention is not limited to following examples.Described method is conventional method if no special instructions.Described material all can obtain from open commercial sources if no special instructions.
The character separation of embodiment 1, triazole type chiral pesticide enantiomers
1. the investigation of Chiral Separation condition
Adopting particle diameter is filling cellulose-3 of 3 μ m, 5-3,5-dimethylphenyl carbamate chirality is the Phenomenex Lux Cellulose-1 chiral chromatographic column of phase fixedly, using acetonitrile/water and methanol/water as mobile phase at reversed-phase liquid chromatography, with the flow velocity of 0.3mL/min and the detection wavelength of 220nm, respectively above-mentioned 9 kinds of Chiral pesticide mappings are split, investigate acetonitrile/water volume ratio and be respectively 90/10, 80/20, 70/30, 60/40, 50/50 and methanol/water volume ratio be respectively 90/10, 85/15, 80/20, 75/25, impact on Chiral Separation in 70/30 o'clock, the results are shown in Table 4 and table 5.
Table 4, triazole type chiral pesticide enantiomers chromatographic resolution parameter
Table 5, Cyproconazole enantiomorph chromatographic resolution parameter
2, the character separation of enantiomorph
With being filled with cellulose-3,5-3,5-dimethylphenyl carbamate chirality fixedly the Phenomenex Lux Cellulose-1 chromatographic column of phase that any one in own azoles alcohol (1), Flutriafol (2), alkene azoles alcohol (3), Cyproconazole (4), fluorine ether azoles (5), epoxiconazole (6), nitrile bacterium azoles (7), RH-7592 (8) and triazolone (9) carried out to liquid chromatography is separated, the eluting order of each enantiomorph when different mobile phase composition that the online polarimetric detector of employing CHIRALYSER-MP type is clear and definite
Chromatographic column used is that particle diameter is filling cellulose-3 of 3 μ m, and 5-3,5-dimethylphenyl carbamate chirality is the Phenomenex Lux Cellulose-1 chiral chromatographic column of phase fixedly, 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, the mixed liquor that the mixed liquor that the acetonitrile that mobile phase is is 60: 40 by volume ratio and water form or the first alcohol and water that is 70: 30 by volume ratio form, the eluting order of own azoles alcohol enantiomorph is followed successively by the own azoles alcohol of dextrorotation and left-handed own azoles alcohol;
In the liquid chromatography separating step of Flutriafol, the mixed liquor that the first alcohol and water that the mixed liquor that the acetonitrile that mobile phase is is 50: 50 by volume ratio and water form or mobile phase are is 70: 30 by volume ratio forms, 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, the mixed liquor that the first alcohol and water that the mixed liquor that the acetonitrile that mobile phase is is 60: 40 by volume ratio and water form or mobile phase are is 75: 25 by volume ratio forms, the eluting order of alkene azoles alcohol enantiomorph is followed successively by left-handed alkene azoles alcohol and d-limonene azoles alcohol;
In the liquid chromatography separating step of Cyproconazole, the mixed liquor that the acetonitrile that mobile phase is is 60: 40 by volume ratio and water form, the eluting order of 4 enantiomorphs of Cyproconazole is followed successively by dextrorotation Cyproconazole, dextrorotation Cyproconazole, left-handed Cyproconazole and left-handed Cyproconazole; Or the mixed liquor that forms for the first alcohol and water that is 70: 30 by volume ratio of mobile phase, 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, the mixed liquor that the acetonitrile that mobile phase is is 80: 20 by volume ratio and water form, 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 epoxiconazole, the mixed liquor that the first alcohol and water that the mixed liquor that the acetonitrile that mobile phase is is 90: 10 by volume ratio and water form or mobile phase are is 90: 10 by volume ratio forms, the eluting order of epoxiconazole enantiomorph is followed successively by left-handed epoxiconazole and dextrorotation epoxiconazole;
In the liquid chromatography separating step of nitrile bacterium azoles, the mixed liquor that the first alcohol and water that the mixed liquor that the acetonitrile that mobile phase is is 90: 10 by volume ratio and water form or mobile phase are is 90: 10 by volume ratio forms, 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, the mixed liquor that the first alcohol and water that the mixed liquor that the acetonitrile that mobile phase is is 90: 10 by volume ratio and water form or mobile phase are is 90: 10 by volume ratio forms, 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, the mixed liquor that the first alcohol and water that the mixed liquor that the acetonitrile that mobile phase is is 50: 50 by volume ratio and water form or mobile phase are is 75: 25 by volume ratio forms, 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; According to the method, carry out the separation of above-mentioned agricultural chemicals, the optically-active eluting order of its degree of separation and every kind of pesticide enantiomers is also listed in table 3.
The optically-active eluting order of table 3, triazole type chiral pesticide enantiomers title, separation condition and enantiomorph
aflutriafol Chiral Separation is not obvious, cannot calculate its degree of separation, but the positive and negative optically-active signal of left-right rotary enantiomorph is obvious.
bthe degree of separation of adjacent two chromatographic peaks, i.e. Rs in 4 chromatographic peaks of Cyproconazole
12/ RsX/Rs
34.In addition, under acetonitrile/water condition, peak 1 and peak 3, peak 2 and peak 4 are respectively a pair of enantiomorphs, under methanol/water condition because eluting order changes peak 1 and peak 2, peak 3 and peak 4 are respectively a pair of enantiomorphs.
The Simultaneous Determination of embodiment 2, triazole type chiral pesticide enantiomers content
1. the foundation of enantiomorph separated in synchronization and LC/MS/MS analytical approach
With the standard solution of 9 kinds of Chiral pesticides, on three grades of quadrupole rod tandem mass spectrometers of API2000 type, carry out the optimization of mass spectrum parameter respectively, comprise the quantitative and qualitative ion pair of selected multiple-reaction monitoring (MRM), impact energy (CE), separate bunch voltage (DP) etc., optimum results is in Table 2.
Table 2, Mass Spectrometer Method condition
Online with liquid chromatography with this understanding, adopt respectively the constant ratio of acetonitrile/water and the chromatographic separation condition of 9 kinds of chiral pesticide enantiomers of gradient elution program optimization, found that adopting gradient elution separation to compare permanent degree wash-out can obtain better Chiral Separation degree and chromatographic peak profile, optimizes selected elution requirement in Table 1.
Table 1, triazole type chiral pesticide enantiomers gradient elution separable programming table
Meanwhile, further optimize the LC/MS/MS detected parameters such as atomization gas, dry gas, collision gas, ionization voltage, finally determine that 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.By the optimization of above-mentioned chromatographic separation condition and the MS detection parameters, formed the Synchronization Analysis instrument method of 9 kinds of chiral pesticide enantiomers provided by the invention, the total ion of typical case with this understanding and each agricultural chemicals extract ion pair chromatogram and see accompanying drawing 1.
2, the foundation of 9 kinds of chiral pesticide enantiomers synchronized analyzing methods in soil
1) prepare pedotheque to be measured:
Take after 20g soil disperses with 2g zeyssatite and add in the 34mL abstraction pool that is added with in advance 0.5g florisil silica, to be usingd mixed liquor that volume ratio forms at 1: 1 by methylene chloride and acetone as extraction solvent, 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 rapid extracting device, circulates 1 time; After extraction, in receiving flask, add 5g anhydrous sodium sulfate to dewater, proceed in the concentrated bottle of 100mL, with merging after extraction solvent wash bottle described in 5mL, 35 ℃ of water-baths are revolved and are steamed to dry, with 1mL, by acetonitrile and water, take the mixed liquor that volume ratio formed as 1: 1 and carry out constant volume, cross after the filter membrane that aperture is 0.22 μ m, obtain pedotheque to be measured.
2) production standard curve:
The potpourri that the standard items that use are 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 the Cyproconazole of 4.35 minutes, retention time is (+) enantiomorph of the Cyproconazole of 5.10 minutes, retention time is (-) enantiomorph of the Cyproconazole of 5.67 minutes, retention time is (-) enantiomorph of the Cyproconazole of 12.51 minutes, (+) enantiomorph of fluorine ether azoles, (-) enantiomorph of fluorine ether azoles, (+) enantiomorph of epoxiconazole, (-) enantiomorph of epoxiconazole, (+) 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 potpourri, the concentration of every kind of enantiomorph is all known.Standard items (being potpourri) are carried out to liquid chromatography-tandem mass spectrometry detection, with separated each enantiomorph, and record every kind of peak area that enantiomorph is corresponding; The concentration value of every kind of enantiomorph of take is independent variable, and take its corresponding peak area is dependent variable, obtains one-variable linear regression equation;
The actual conditions of liquid chromatography detecting method is: chromatographic column is for loading cellulose-3, and 5-3,5-dimethylphenyl carbamate is the Phenomenex Lux Cellulose-1 chromatographic column of phase fixedly, and length is 150 millimeters, and internal diameter is 2.0 millimeters, and sample size is 10 μ L; The mixed solution that the elution buffer using is acetonitrile and water, type of elution is gradient elution, elution speed is 0.3mL/min;
Described gradient elution mode following (also as shown in table 1):
1min rises to 6min end, and in mixed solution, the volume ratio of water and acetonitrile is 50%: 50%;
7min rises to 10min end, and in mixed solution, the volume ratio of water and acetonitrile is 30%: 70%;
11min rises to 18min end, and in mixed solution, the volume ratio of water and acetonitrile is 50%: 50%;
Table 1, liquid phase chromatogram condition
According to the method for each eluting peak of mass-to-charge ratio character separation of eluting peak retention time and parent ion/daughter ion following (also as shown in table 2):
The mass-to-charge ratio of parent ion/daughter ion that retention time is 5.72 minutes, quantitatively detect is (+) enantiomorph that eluting peak that the mass-to-charge ratio of the parent ion/daughter ion of 314.4/70.0 and qualitative detection is 314.4/159.0 is own azoles alcohol;
The mass-to-charge ratio of parent ion/daughter ion that retention time is 6.50 minutes, quantitatively detect is (-) enantiomorph that eluting peak that the mass-to-charge ratio of the parent ion/daughter ion of 314.4/70.0 and qualitative detection is 314.4/159.0 is own azoles alcohol;
The mass-to-charge ratio of parent ion/daughter ion that retention time is 3.27 minutes, quantitatively detect is (-) enantiomorph that eluting peak that the mass-to-charge ratio of the parent ion/daughter ion of 302.1/70.0 and qualitative detection is 302.1/123.1 is Flutriafol;
The mass-to-charge ratio of parent ion/daughter ion that retention time is 3.47 minutes, quantitatively detect is (+) enantiomorph that eluting peak that the mass-to-charge ratio of the parent ion/daughter ion of 302.1/70.0 and qualitative detection is 302.1/123.1 is Flutriafol;
The mass-to-charge ratio of parent ion/daughter ion that retention time is 6.48 minutes, quantitatively detect is (-) enantiomorph that eluting peak that the mass-to-charge ratio of the parent ion/daughter ion of 326.1/70.0 and qualitative detection is 326.1/159.0 is alkene azoles alcohol;
The mass-to-charge ratio of parent ion/daughter ion that retention time is 6.97 minutes, quantitatively detect is (-) enantiomorph that eluting peak that the mass-to-charge ratio of the parent ion/daughter ion of 326.1/70.0 and qualitative detection is 326.1/159.0 is alkene azoles alcohol;
The mass-to-charge ratio of parent ion/daughter ion that retention time is 4.35 minutes, quantitatively detect is (+) enantiomorph that eluting peak that the mass-to-charge ratio of the parent ion/daughter ion of 292.2/70.0 and qualitative detection is 292.2/125.0 is Cyproconazole;
The mass-to-charge ratio of parent ion/daughter ion that retention time is 5.10 minutes, quantitatively detect is (+) enantiomorph that eluting peak that the mass-to-charge ratio of the parent ion/daughter ion of 292.2/70.0 and qualitative detection is 292.2/125.0 is Cyproconazole;
The mass-to-charge ratio of parent ion/daughter ion that retention time is 5.67 minutes, quantitatively detect is (-) enantiomorph that eluting peak that the mass-to-charge ratio of the parent ion/daughter ion of 292.2/70.0 and qualitative detection is 292.2/125.0 is Cyproconazole;
The mass-to-charge ratio of parent ion/daughter ion that retention time is 12.51 minutes, quantitatively detect is (-) enantiomorph that eluting peak that the mass-to-charge ratio of the parent ion/daughter ion of 292.2/70.0 and qualitative detection is 292.2/125.0 is Cyproconazole;
The mass-to-charge ratio of parent ion/daughter ion that retention time is 6.99 minutes, quantitatively detect is (+) enantiomorph that eluting peak that the mass-to-charge ratio of the parent ion/daughter ion of 372.2/159.0 and qualitative detection is 372.2/70.0 is fluorine ether azoles;
The mass-to-charge ratio of parent ion/daughter ion that retention time is 8.52 minutes, quantitatively detect is (-) enantiomorph that eluting peak that the mass-to-charge ratio of the parent ion/daughter ion of 372.2/159.0 and qualitative detection is 372.2/70.0 is fluorine ether azoles;
The mass-to-charge ratio of parent ion/daughter ion that retention time is 7.14 minutes, quantitatively detect is (-) enantiomorph that eluting peak that the mass-to-charge ratio of the parent ion/daughter ion of 330.3/121.2 and qualitative detection is 330.3/123.2 is epoxiconazole;
The mass-to-charge ratio of parent ion/daughter ion that retention time is 11.59 minutes, quantitatively detect is (+) enantiomorph that eluting peak that the mass-to-charge ratio of the parent ion/daughter ion of 330.3/121.2 and qualitative detection is 330.3/123.2 is epoxiconazole;
The mass-to-charge ratio of parent ion/daughter ion that retention time is 6.05 minutes, quantitatively detect is (+) enantiomorph that eluting peak that the mass-to-charge ratio of the parent ion/daughter ion of 289.2/70.0 and qualitative detection is 289.2/125.0 is nitrile bacterium azoles;
The mass-to-charge ratio of parent ion/daughter ion that retention time is 7.77 minutes, quantitatively detect is (-) enantiomorph that eluting peak that the mass-to-charge ratio of the parent ion/daughter ion of 289.2/70.0 and qualitative detection is 289.2/125.0 is nitrile bacterium azoles;
The mass-to-charge ratio of parent ion/daughter ion that retention time is 10.66 minutes, quantitatively detect is (+) enantiomorph that eluting peak that the mass-to-charge ratio of the parent ion/daughter ion of 337.2/70.0 and qualitative detection is 337.2/125.0 is RH-7592;
The mass-to-charge ratio of parent ion/daughter ion that retention time is 11.66 minutes, quantitatively detect is (-) enantiomorph that eluting peak that the mass-to-charge ratio of the parent ion/daughter ion of 337.2/70.0 and qualitative detection is 337.2/125.0 is RH-7592;
The mass-to-charge ratio of parent ion/daughter ion that retention time is 5.02 minutes, quantitatively detect is (-) enantiomorph that eluting peak that the mass-to-charge ratio of the parent ion/daughter ion of 294.1/197.1 and qualitative detection is 294.1/69.1 is triazolone;
The mass-to-charge ratio of parent ion/daughter ion that retention time is 5.61 minutes, quantitatively detect is (+) enantiomorph that eluting peak that the mass-to-charge ratio of the parent ion/daughter ion of 294.1/197.1 and qualitative detection is 294.1/69.1 is triazolone.
Tandem mass spectrum testing conditions is as follows: electron spray ionisation source atomization gas pressure is 15psi, and dry gas is 55psi, and collision atmospheric pressure is 3psi, be+5500V of ionization voltage, and ion source temperature is 400 ℃;
Every kind of solution bunch voltage, impact energy following (also as shown in table 2) that enantiomorph is corresponding:
(+) 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 epoxiconazole: separating bunch voltage is 25, and impact energy is 30;
(+) enantiomorph of epoxiconazole: 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 obtaining is as shown in table 6,
The linear equation of table 6, triazole type chiral pesticide enantiomers
3) detect pedotheque to be measured
According to step 2) identical method carries out separatedly, only potpourri standard items replaced to step 1) gained pedotheque to be measured, and record every kind of peak area that enantiomorph is corresponding;
4) by every kind of peak area substitution step 2 that enantiomorph is corresponding) in one-variable linear regression equation, obtain the concentration of every kind of enantiomorph in testing sample, complete the mensuration of triazole type chiral pesticide enantiomers content in pedotheque to be measured.
3, the accuracy of Simultaneous Determination said method, repeatability and sensitivity detect
For evaluating accuracy, repeatability and the sensitivity of this Simultaneous Determination method, take the blank pedotheque of 20g, add respectively certain density hybrid standard sample, after mixing, form the pedotheque of different interpolation levels, after processing by above-mentioned agent, soil treatment method, upper machine is measured, and the results are shown in Table 7.
Table 7, triazole type chiral pesticide enantiomers soil add measurement result
As shown in Table 7, in soil, the enantiomorph of the 9 kinds of triazole type Chiral pesticides interpolation recovery and repeatability are all better, low according to the method detectability of 3 times of signal to noise ratio (S/N ratio) gained, detect and be limited to 0.5-1.0 μ g/kg, be applicable to the how residual synchronous detection of above-mentioned chiral pesticide enantiomers in ambient soil.
Claims (6)
1. a method for separated triazole type chiral pesticide enantiomers from sample, comprises the steps:
Testing sample is carried out to liquid chromatography-tandem mass spectrometry detection, according to eluting peak retention time and the mass-to-charge ratio of parent ion/daughter ion quantitatively detecting and each eluting peak of mass-to-charge ratio character separation of the parent ion/daughter ion of qualitative detection, obtain each triazole type chiral pesticide enantiomers;
Described triazole type Chiral pesticide is comprised of following compound: own azoles alcohol, Flutriafol, alkene azoles alcohol, Cyproconazole, fluorine ether azoles, epoxiconazole, nitrile bacterium azoles, RH-7592 and triazolone; The condition of described liquid chromatographic detection is as follows: chromatographic column is for loading cellulose-3, and 5-3,5-dimethylphenyl carbamate is the Phenomenex Lux Cellulose-1 chromatographic column of phase fixedly; The mixed solution that the eluent using is acetonitrile and water, type of elution is gradient elution, elution speed is 0.3mL/min;
Described gradient elution mode is as follows:
1min rises to 6min end, and in mixed solution, the volume ratio of water and acetonitrile is 50%:50%;
7min rises to 10min end, and in mixed solution, the volume ratio of water and acetonitrile is 30%:70%;
11min rises to 18min end, and in mixed solution, the volume ratio of water and acetonitrile is 50%:50%;
The described method according to each eluting peak of mass-to-charge ratio character separation of eluting peak retention time and parent ion/daughter ion is as follows:
The mass-to-charge ratio of parent ion/daughter ion that retention time is 5.72 minutes, quantitatively detect is (+) enantiomorph that eluting peak that the mass-to-charge ratio of the parent ion/daughter ion of 314.4/70.0 and qualitative detection is 314.4/159.0 is own azoles alcohol;
The mass-to-charge ratio of parent ion/daughter ion that retention time is 6.50 minutes, quantitatively detect is (-) enantiomorph that eluting peak that the mass-to-charge ratio of the parent ion/daughter ion of 314.4/70.0 and qualitative detection is 314.4/159.0 is own azoles alcohol;
The mass-to-charge ratio of parent ion/daughter ion that retention time is 3.27 minutes, quantitatively detect is (-) enantiomorph that eluting peak that the mass-to-charge ratio of the parent ion/daughter ion of 302.1/70.0 and qualitative detection is 302.1/123.1 is Flutriafol;
The mass-to-charge ratio of parent ion/daughter ion that retention time is 3.47 minutes, quantitatively detect is (+) enantiomorph that eluting peak that the mass-to-charge ratio of the parent ion/daughter ion of 302.1/70.0 and qualitative detection is 302.1/123.1 is Flutriafol;
The mass-to-charge ratio of parent ion/daughter ion that retention time is 6.48 minutes, quantitatively detect is (-) enantiomorph that eluting peak that the mass-to-charge ratio of the parent ion/daughter ion of 326.1/70.0 and qualitative detection is 326.1/159.0 is alkene azoles alcohol;
The mass-to-charge ratio of parent ion/daughter ion that retention time is 6.97 minutes, quantitatively detect is (+) enantiomorph that eluting peak that the mass-to-charge ratio of the parent ion/daughter ion of 326.1/70.0 and qualitative detection is 326.1/159.0 is alkene azoles alcohol;
The mass-to-charge ratio of parent ion/daughter ion that retention time is 4.35 minutes, quantitatively detect is (+) enantiomorph that eluting peak that the mass-to-charge ratio of the parent ion/daughter ion of 292.2/70.0 and qualitative detection is 292.2/125.0 is Cyproconazole;
The mass-to-charge ratio of parent ion/daughter ion that retention time is 5.10 minutes, quantitatively detect is (+) enantiomorph that eluting peak that the mass-to-charge ratio of the parent ion/daughter ion of 292.2/70.0 and qualitative detection is 292.2/125.0 is Cyproconazole;
The mass-to-charge ratio of parent ion/daughter ion that retention time is 5.67 minutes, quantitatively detect is (-) enantiomorph that eluting peak that the mass-to-charge ratio of the parent ion/daughter ion of 292.2/70.0 and qualitative detection is 292.2/125.0 is Cyproconazole;
The mass-to-charge ratio of parent ion/daughter ion that retention time is 12.51 minutes, quantitatively detect is (-) enantiomorph that eluting peak that the mass-to-charge ratio of the parent ion/daughter ion of 292.2/70.0 and qualitative detection is 292.2/125.0 is Cyproconazole;
The mass-to-charge ratio of parent ion/daughter ion that retention time is 6.99 minutes, quantitatively detect is (+) enantiomorph that eluting peak that the mass-to-charge ratio of the parent ion/daughter ion of 372.2/159.0 and qualitative detection is 372.2/70.0 is fluorine ether azoles;
The mass-to-charge ratio of parent ion/daughter ion that retention time is 8.52 minutes, quantitatively detect is (-) enantiomorph that eluting peak that the mass-to-charge ratio of the parent ion/daughter ion of 372.2/159.0 and qualitative detection is 372.2/70.0 is fluorine ether azoles;
The mass-to-charge ratio of parent ion/daughter ion that retention time is 7.14 minutes, quantitatively detect is (-) enantiomorph that eluting peak that the mass-to-charge ratio of the parent ion/daughter ion of 330.3/121.2 and qualitative detection is 330.3/123.2 is epoxiconazole;
The mass-to-charge ratio of parent ion/daughter ion that retention time is 11.59 minutes, quantitatively detect is (+) enantiomorph that eluting peak that the mass-to-charge ratio of the parent ion/daughter ion of 330.3/121.2 and qualitative detection is 330.3/123.2 is epoxiconazole;
The mass-to-charge ratio of parent ion/daughter ion that retention time is 6.05 minutes, quantitatively detect is (+) enantiomorph that eluting peak that the mass-to-charge ratio of the parent ion/daughter ion of 289.2/70.0 and qualitative detection is 289.2/125.0 is nitrile bacterium azoles;
The mass-to-charge ratio of parent ion/daughter ion that retention time is 7.77 minutes, quantitatively detect is (-) enantiomorph that eluting peak that the mass-to-charge ratio of the parent ion/daughter ion of 289.2/70.0 and qualitative detection is 289.2/125.0 is nitrile bacterium azoles;
The mass-to-charge ratio of parent ion/daughter ion that retention time is 10.66 minutes, quantitatively detect is (+) enantiomorph that eluting peak that the mass-to-charge ratio of the parent ion/daughter ion of 337.2/70.0 and qualitative detection is 337.2/125.0 is RH-7592;
The mass-to-charge ratio of parent ion/daughter ion that retention time is 11.66 minutes, quantitatively detect is (-) enantiomorph that eluting peak that the mass-to-charge ratio of the parent ion/daughter ion of 337.2/70.0 and qualitative detection is 337.2/125.0 is RH-7592;
The mass-to-charge ratio of parent ion/daughter ion that retention time is 5.02 minutes, quantitatively detect is (-) enantiomorph that eluting peak that the mass-to-charge ratio of the parent ion/daughter ion of 294.1/197.1 and qualitative detection is 294.1/69.1 is triazolone;
The mass-to-charge ratio of parent ion/daughter ion that retention time is 5.61 minutes, quantitatively detect is (+) enantiomorph that eluting peak that the mass-to-charge ratio of the parent ion/daughter ion of 294.1/197.1 and qualitative detection is 294.1/69.1 is triazolone;
Described from sample the method for separated triazole type chiral pesticide enantiomers, also comprise the step of testing sample being carried out to pre-treatment;
The method of described pre-treatment comprises the steps: to take after 20g testing sample disperses with 2g zeyssatite and adds in the 34mL abstraction pool that is added with in advance 0.5g florisil silica, to be usingd mixed liquor that volume ratio 1:1 forms by methylene chloride and acetone as extraction solvent, 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 rapid extracting device, circulates 1 time; After extraction, in receiving flask, add 5g anhydrous sodium sulfate to dewater, proceed in the concentrated bottle of 100mL, with merging after extraction solvent wash bottle described in 5mL, 35 ℃ of water-baths are revolved and are steamed to dry, with 1mL, by acetonitrile and water, take volume ratio and carry out constant volume as the mixed liquor that 1:1 forms, cross after the filter membrane that aperture is 0.22 μ m, obtain testing sample extract; Described testing sample is soil;
In described Mass Spectrometer Method condition, electron spray ionisation source atomization gas pressure is 15psi, and dry gas is 55psi, and collision atmospheric pressure is 3psi, be+5500V of ionization voltage, and ion source temperature is 400 ℃;
Solution bunch voltage, impact energy that every kind of enantiomorph is corresponding are as follows:
(+) enantiomorph of own azoles alcohol: separating bunch voltage is 25V, and impact energy is 35V;
(-) enantiomorph of own azoles alcohol: separating bunch voltage is 25V, and impact energy is 35V;
(-) enantiomorph of Flutriafol: separating bunch voltage is 25V, and impact energy is 35V;
(+) enantiomorph of Flutriafol: separating bunch voltage is 25V, and impact energy is 35V;
(-) enantiomorph of alkene azoles alcohol: separating bunch voltage is 25V, and impact energy is 35V;
(+) enantiomorph of alkene azoles alcohol: separating bunch voltage is 25V, and impact energy is 35V;
(+) enantiomorph of Cyproconazole: separating bunch voltage is 25V, and impact energy is 35V;
(+) enantiomorph of Cyproconazole: separating bunch voltage is 25V, and impact energy is 35V;
(-) enantiomorph of Cyproconazole: separating bunch voltage is 25V, and impact energy is 35V;
(-) enantiomorph of Cyproconazole: separating bunch voltage is 25V, and impact energy is 35V;
(+) enantiomorph of fluorine ether azoles: separating bunch voltage is 20V, and impact energy is 30V;
(-) enantiomorph of fluorine ether azoles: separating bunch voltage is 20V, and impact energy is 35V;
(-) enantiomorph of epoxiconazole: separating bunch voltage is 25V, and impact energy is 30V;
(+) enantiomorph of epoxiconazole: separating bunch voltage is 25V, and impact energy is 30V;
(+) enantiomorph of nitrile bacterium azoles: separating bunch voltage is 25V, and impact energy is 35V;
(-) enantiomorph of nitrile bacterium azoles: separating bunch voltage is 20V, and impact energy is 40V;
(+) enantiomorph of RH-7592: separating bunch voltage is 25V, and impact energy is 35V;
(-) enantiomorph of RH-7592: separating bunch voltage is 20V, and impact energy is 35V;
(-) enantiomorph of triazolone: separating bunch voltage is 25V, and impact energy is 25V;
(+) enantiomorph of triazolone: separating bunch voltage is 25V, and impact energy is 30V.
2. method according to claim 1, is characterized in that: in the testing conditions of described liquid chromatography, the length of described chromatographic column is 150 millimeters, and internal diameter is 2.0 millimeters; Sample size is 10 μ L; Described cellulose-3, the particle diameter of 5-3,5-dimethylphenyl carbamate is 3 μ m.
3. a method that detects triazole type chiral pesticide enantiomers content in sample, comprises the steps:
1) the triazole type chiral pesticide enantiomers standard items of concentration known are mixed and carry out separation according to method described in claim 1 or 2, and record every kind of peak area that enantiomorph is corresponding; The concentration value of every kind of enantiomorph of take is independent variable, and take its corresponding peak area is dependent variable, obtains one-variable linear regression equation;
2) testing sample is carried out to separation according to method described in claim 1 or 2, and record every kind of peak area that enantiomorph is corresponding;
3), by every kind of middle one-variable linear regression equation of peak area substitution step (1) that enantiomorph is corresponding, obtain the concentration of enantiomorph in described testing sample;
Described triazole type Chiral pesticide is comprised of following compound: own azoles alcohol, Flutriafol, alkene azoles alcohol, Cyproconazole, fluorine ether azoles, epoxiconazole, nitrile bacterium azoles, RH-7592 and triazolone, described triazole type chiral pesticide enantiomers standard items are comprised of 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 the Cyproconazole of 4.35 minutes, retention time is (+) enantiomorph of the Cyproconazole of 5.10 minutes, retention time is (-) enantiomorph of the Cyproconazole of 5.67 minutes, retention time is (-) enantiomorph of the Cyproconazole of 12.51 minutes, (+) enantiomorph of fluorine ether azoles, (-) enantiomorph of fluorine ether azoles, (+) enantiomorph of epoxiconazole, (-) enantiomorph of epoxiconazole, (+) 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 described detection sample, the method for triazole type chiral pesticide enantiomers content, also comprises the step of testing sample being carried out to pre-treatment;
The method of described pre-treatment comprises the steps: to take after 20g testing sample disperses with 2g zeyssatite and adds in the 34mL abstraction pool that is added with in advance 0.5g florisil silica, to be usingd mixed liquor that volume ratio 1:1 forms by methylene chloride and acetone as extraction solvent, 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 rapid extracting device, circulates 1 time; After extraction, in receiving flask, add 5g anhydrous sodium sulfate to dewater, proceed in the concentrated bottle of 100mL, with merging after extraction solvent wash bottle described in 5mL, 35 ℃ of water-baths are revolved and are steamed to dry, with 1mL, by acetonitrile and water, take volume ratio and carry out constant volume as the mixed liquor that 1:1 forms, cross after the filter membrane that aperture is 0.22 μ m, obtain testing sample extract; Described testing sample is soil.
4. method according to claim 3, is characterized in that: the one-variable linear regression equation of described various enantiomorphs is as follows:
(+) enantiomorph of own azoles alcohol: y=541x+1700, independent variable concentration range is 25～500 μ g/L;
(-) enantiomorph of own azoles alcohol: y=526x+1680, independent variable concentration range is 25～500 μ g/L;
(+) enantiomorph of Flutriafol: y=844x – 38.4, independent variable concentration range is 25～500 μ g/L;
Flutriafol (-) enantiomorph: y=725x – 1210, independent variable concentration range is 25～500 μ g/L;
(+) enantiomorph of alkene azoles alcohol: y=292x+1630, independent variable concentration range is 25～500 μ g/L;
(-) enantiomorph of alkene azoles alcohol: y=274x+253, independent variable concentration range is 25～500 μ g/L;
Retention time is (+) enantiomorph of the Cyproconazole of 4.35 minutes: y=965x+378, and independent variable concentration range is 9～180 μ g/L;
Retention time is (+) enantiomorph of the Cyproconazole of 5.10 minutes: y=951x+571, and independent variable concentration range is 16～320 μ g/L;
Retention time is (-) enantiomorph of the Cyproconazole of 5.67 minutes: y=930x+259, and independent variable concentration range is 9～180 μ g/L;
Retention time is (-) enantiomorph of the Cyproconazole of 12.51 minutes: y=725x+877, and independent variable concentration range is 16～320 μ g/L;
(+) enantiomorph of fluorine ether azoles: y=344x+2710, independent variable concentration range is 25～500 μ g/L;
(-) enantiomorph of fluorine ether azoles: y=395x+414, independent variable concentration range is 25～500 μ g/L;
(+) enantiomorph of epoxiconazole: y=694x+1700, independent variable concentration range is 25～500 μ g/L;
(-) enantiomorph of epoxiconazole: y=724x+2280, independent variable concentration range is 25～500 μ g/L;
(+) enantiomorph of nitrile bacterium azoles: y=337x+1590, independent variable concentration range is 25～500 μ g/L;
(-) enantiomorph of nitrile bacterium azoles: y=353x+264, independent variable concentration range is 25～500 μ g/L;
(+) enantiomorph of RH-7592: y=215x-857, independent variable concentration range is 25～500 μ g/L;
(-) enantiomorph of RH-7592: y=199x+400, independent variable concentration range is 25～500 μ g/L;
(+) enantiomorph of triazolone: y=318x+2570, independent variable concentration range is 25～500 μ g/L;
(-) enantiomorph of triazolone: y=319x+1830, independent variable concentration range is 25～500 μ g/L.
5. the character separation method of a triazole type chiral pesticide enantiomers, comprise the steps: with loading cellulose-3,5-3,5-dimethylphenyl carbamate chirality fixedly the Phenomenex Lux Cellulose-1 chromatographic column of phase that own azoles alcohol, Flutriafol, alkene azoles alcohol, Cyproconazole, fluorine ether azoles, epoxiconazole, nitrile bacterium azoles, RH-7592 and triazolone are carried out to liquid chromatography is separated
Wherein, in the liquid chromatography separating step of own azoles alcohol, the mixed liquor that the mixed liquor that the acetonitrile that mobile phase is is 60:40 by volume ratio and water form or the first alcohol and water that is 70:30 by volume ratio form, the eluting order of own azoles alcohol enantiomorph is followed successively by the own azoles alcohol of dextrorotation and left-handed own azoles alcohol;
In the liquid chromatography separating step of Flutriafol, the mixed liquor that the first alcohol and water that the mixed liquor that the acetonitrile that mobile phase is is 50:50 by volume ratio and water form or mobile phase are is 70:30 by volume ratio forms, 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, the mixed liquor that the first alcohol and water that the mixed liquor that the acetonitrile that mobile phase is is 60:40 by volume ratio and water form or mobile phase are is 75:25 by volume ratio forms, the eluting order of alkene azoles alcohol enantiomorph is followed successively by left-handed alkene azoles alcohol and d-limonene azoles alcohol;
In the liquid chromatography separating step of Cyproconazole, the mixed liquor that the acetonitrile that mobile phase is is 60:40 by volume ratio and water form, the eluting order of 4 enantiomorphs of Cyproconazole is followed successively by dextrorotation Cyproconazole, dextrorotation Cyproconazole, left-handed Cyproconazole and left-handed Cyproconazole; Or the mixed liquor that forms for the first alcohol and water that is 70:30 by volume ratio of mobile phase, 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, the mixed liquor that the acetonitrile that mobile phase is is 80:20 by volume ratio and water form, 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 epoxiconazole, the mixed liquor that the first alcohol and water that the mixed liquor that the acetonitrile that mobile phase is is 90:10 by volume ratio and water form or mobile phase are is 90:10 by volume ratio forms, the eluting order of epoxiconazole enantiomorph is followed successively by left-handed epoxiconazole and dextrorotation epoxiconazole;
In the liquid chromatography separating step of nitrile bacterium azoles, the mixed liquor that the first alcohol and water that the mixed liquor that the acetonitrile that mobile phase is is 90:10 by volume ratio and water form or mobile phase are is 90:10 by volume ratio forms, 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, the mixed liquor that the first alcohol and water that the mixed liquor that the acetonitrile that mobile phase is is 90:10 by volume ratio and water form or mobile phase are is 90:10 by volume ratio forms, 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, the mixed liquor that the first alcohol and water that the mixed liquor that the acetonitrile that mobile phase is is 50:50 by volume ratio and water form or mobile phase are is 75:25 by volume ratio forms, the eluting order of triazolone enantiomorph is followed successively by left-handed triazolone and dextrorotation triazolone.
6. method according to claim 5, it is characterized in that: described filling cellulose-3,5-3,5-dimethylphenyl carbamate chirality is fixedly in the Phenomenex Lux Cellulose-1 chromatographic column of phase, described cellulose-3, the particle diameter of 5-3,5-dimethylphenyl carbamate chirality fixed phase stuffing is 3 μ m, the length of described 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 CN102353740A (en) | 2012-02-15 |
| CN102353740B true 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) |
Families Citing this family (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 |
| CN105259289B (en) * | 2015-11-02 | 2017-05-17 | 南京大学 | Recognition method of toxic chiral monomers in triazole fungicide waste water |
| 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 |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101358953B (en) * | 2008-09-18 | 2011-12-07 | 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
Non-Patent Citations (8)
| Title |
|---|
| Determination of multiclass pesticides in food commodities By pressurized liquid extraction using GC–MS/MS and LC–MS/MS;Garrido Frenich A. et al，;《Anal Bioanal Chem》;20051103;第383卷(第11期);1106-1118 * |
| Enantiomeric separation of chiral pesticides by high Performance liquid chromatography on cellulose tris-3,5-dimethyl carbamate stationary phase under reversed phase conditions;Qin Tian et al，;《Journal of separation science》;20070213;第30卷(第3期);310-321 * |
| 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》.1997,第122卷895-898. * |
| Qiu Jing et al,.Enantiomeric Separation of Triazole Fungicides with 3-µm and 5-µm Particle Chiral Columns by Reverse-Phase High-Performance.《Chirality》.2011,第23卷(第6期),479-486. * |
| 三唑醇对映体的反相高效液相色谱拆分热力学研究;王新全 等，;《农药学学报》;20110131;第13卷(第1期);53-58 * |
| 反相色谱条件下三唑类手性农药对映异构体的拆分;田芹 等，;《分析化学研究简报》;20100531;第38卷(第5期);688-692 * |
| 王鹏 等,.手性农药及对映体分析.《第九届全国农药质量管理与分析技术交流会论文集》.2008,94-103. * |
| 程莉.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.《中国优秀硕士学位论文全文数据库农业科技辑》.2011,16-46. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102353740A (en) | 2012-02-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102353740B (en) | Method for synchronous determination of content of triazole chiral pesticide enantiomers | |
| Li et al. | Simultaneous enantioselective determination of triazole fungicides in soil and water by chiral liquid chromatography/tandem mass spectrometry | |
| Gerssen et al. | Screening of lipophilic marine toxins in shellfish and algae: Development of a library using liquid chromatography coupled to orbitrap mass spectrometry | |
| CN102735784B (en) | Method for simultaneously determining one hundred pesticide residuals in traditional Chinese medicine through ultrahigh performance liquid chromatography-tandem quadrupole mass spectrum | |
| Li et al. | Simultaneous enantioselective determination of fenbuconazole and its main metabolites in soil and water by chiral liquid chromatography/tandem mass spectrometry | |
| CN106841471A (en) | It is a kind of while determining 12 kinds of methods of OPEs residuals in water sample and deposit | |
| CN103529155B (en) | The assay method of wood preservation agent content in a kind of Wood children articles for use | |
| Jones et al. | Investigating sub-2 μm particle stationary phase supercritical fluid chromatography coupled to mass spectrometry for chemical profiling of chamomile extracts | |
| Guan et al. | Modified QuEChERS method for the analysis of 11 pesticide residues in tea by liquid chromatography–tandem mass spectrometry | |
| CN107727760A (en) | A kind of assay method of Pesticides in Tea medicine enantiomter residual quantity | |
| Marchal et al. | Development of an analytical methodology using Fourier transform mass spectrometry to discover new structural analogs of wine natural sweeteners | |
| Celano et al. | Liquid chromatography quadrupole time-of-flight mass spectrometry quantification and screening of organophosphate compounds in sludge | |
| 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 | |
| Zhang et al. | Rapid gas chromatography with flame photometric detection of multiple organophosphorus pesticides in Salvia miltiorrhizae after ultrasonication assisted one-step extraction | |
| Jin et al. | Ion chromatography-atmospheric pressure chemical ionization mass spectrometry for the determination of trace chlorophenols in clam tissues | |
| 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 | |
| Zhang et al. | Efficient separation determination of protopanaxatriol ginsenosides Rg1, Re, Rf, Rh1, Rg2 by HPLC | |
| CN105954422A (en) | Method for quick detection of content of citrinin in traditional Chinese medicinal materials | |
| 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 | |
| Dou et al. | Carbon nanotube-based QuEChERS extraction and enhanced product ion scan-assisted confirmation of multi-pesticide residue in dried tangerine peel | |
| CN108426972B (en) | Method for splitting and measuring chiral pesticide benalaxyl enantiomer by ultra-high performance combined chromatography-tandem mass spectrometry technology | |
| Martínez et al. | Determination of pyrethroid insecticides in vegetables with liquid chromatography using detection by electrospray mass spectrometry | |
| Zhao et al. | Development and validation of a selective and effective pressurized liquid extraction followed by liquid chromatography–mass spectrometry method for the determination of fructosazine analogues in the ammonia treated extract of Eugenia jambolana Lamarck seeds | |
| Kanda et al. | Rapid determination of nitroimidazole residues in honey by liquid chromatography/tandem 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 |