CN108037218A - The method of 5a,6,9,9a-hexahydro-6,9-methano-2,4 in gas chromatography tandem mass spectrometry method measure feed - Google Patents
The method of 5a,6,9,9a-hexahydro-6,9-methano-2,4 in gas chromatography tandem mass spectrometry method measure feed Download PDFInfo
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- CN108037218A CN108037218A CN201810056904.4A CN201810056904A CN108037218A CN 108037218 A CN108037218 A CN 108037218A CN 201810056904 A CN201810056904 A CN 201810056904A CN 108037218 A CN108037218 A CN 108037218A
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- G—PHYSICS
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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- G01N30/02—Column chromatography
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Abstract
The method that the present invention discloses 5a,6,9,9a-hexahydro-6,9-methano-2,4 in a kind of gas-chromatography tandem mass spectrometry measure feed, this method include sample pre-treatments and detecting step；It is to weigh a certain amount of sample, after the 5a,6,9,9a-hexahydro-6,9-methano-2,4 in sample is extracted using organic solvent trifluoroacetic acid aqueous solution as extraction agent, nitrogen evaporator concentrates, and concentrate is purified through Florisil diatomite SPE solid-phase extraction columns, then legal and quantitative with gas-chromatography tandem mass spectrum.The present invention is easy and time-consuming short through Florisil SPE Solid Phase Extraction column purifications, the pre-treatment after concentration using organic solvent trifluoroacetic acid aqueous solution as extractant；Gas-chromatography tandem mass spectrometry takes more reaction detections（MRM）Pattern is measured, and sensitivity and precision are high, qualitative and quantitative accurate；The method universality of the present invention is strong, suitable for the Feed Sample of assistant ingredients, disclosure satisfy that the quick separating of 5a,6,9,9a-hexahydro-6,9-methano-2,4 and detection in Feed Sample.
Description
Technical field
The present invention relates to a kind of method for measuring pesticide residual sulphur pellet in feed, especially for this complex matrices of feed
Pre-treatment and gas chromatography tandem mass spectrometry detection method.
Background technology
With the development of poultry industry, Feed Manufacturing amount is also substantially improved, and feed production quality also receives much concern.All can every year
Since the pesticide of animal products, residue of veterinary drug problem influence its export volume.The raw material of feed is essentially from crops, therefore feed
Pesticide residue be to cause the principal element of animal products pesticide residue.Pesticide residue in feed not only has cause to livestock and poultry
Poison, teratogenesis, carcinogenic etc. influence, and enter human body harm health by animal products.By controlling major source feed pesticide
Residual is the remaining fine means of pesticide in control animal products, so Detecting Pesticide just seems very necessary in feed.
5a,6,9,9a-hexahydro-6,9-methano-2,4 is mainly used for agricultural insecticide, is commonly used to the pest of the crops such as prevention cereal, veterinary antibiotics.5a,6,9,9a-hexahydro-6,9-methano-2,4 is as having
Machine chlorine insecticides not only have the characteristics that hypertoxicity, bioconcentration, but also stable structure, the time degraded in the environment
It is long.Residual secretion of the 5a,6,9,9a-hexahydro-6,9-methano-2,4 to body effect's central nervous system, immune function and hormone in the environment, and thus by《This
De Geermo pacts》It is classified as banned substance.
At present, 5a,6,9,9a-hexahydro-6,9-methano-2,4 quantitative detecting method mainly includes：Near-infrared quick determination method, enzyme-linked immunization, gas-chromatography
The methods of method, gas chromatography-mass spectrography.5a,6,9,9a-hexahydro-6,9-methano-2,4 detection in all multi-methods is directed to tealeaves, veterinary antibiotics and aquatic products
Matrix, but seldom had been reported that at present for 5a,6,9,9a-hexahydro-6,9-methano-2,4 detection in feed substrate.Gas chromatography tandem mass spectrometry is due to its interference resistance
Strong qualitative reliable and high sensitivity performance is stablized, quantitative to be accurately widely used in the residual detection of agriculture.
The content of the invention
The purpose of the present invention is：The method for designing 5a,6,9,9a-hexahydro-6,9-methano-2,4 in a kind of gas chromatography tandem mass spectrometry method measure feed, for feeding
Material matrix uses the small column purifications of florisil silica SPE, and 5a,6,9,9a-hexahydro-6,9-methano-2,4 content, the method processing consumption are measured with gas chromatography tandem mass spectrometry
When it is short, consumptive material price is low, and can be very good that 5a,6,9,9a-hexahydro-6,9-methano-2,4 in feed is extracted and purified；Gas chromatography tandem mass spectrometry selection at the same time
Ion scan parameter can accurately detect 5a,6,9,9a-hexahydro-6,9-methano-2,4 content, and the gas chromatography tandem mass spectrometry method of foundation measures 5a,6,9,9a-hexahydro-6,9-methano-2,4 method in feed
Pre-treatment is quick, simple, detection limit is low (1 μ g/kg), and accuracy and precision are high.
The present invention technical solution be：The method of 5a,6,9,9a-hexahydro-6,9-methano-2,4 includes in gas chromatography tandem mass spectrometry method measure feed
Sample pre-treatments and detecting step；It is characterized in that：The sample pre-treatments step is：A certain amount of sample is weighed, with organic
After solvent trifluoroacetic acid aqueous solution extracts the 5a,6,9,9a-hexahydro-6,9-methano-2,4 in sample for extraction agent, nitrogen evaporator concentration, using Fu Luoli diatomite SPE solid phases
Extraction column purifies concentrate；The detecting step is：Purified prepare liquid, using gas chromatography tandem mass spectrometry
Separate and detect, more reaction detections（MRM）Pattern carries out qualitative and quantitative.
Wherein, the sample pre-treatments comprise the concrete steps that：
（1）Prepare sample：Take feed to be crushed with pulverizer, cross 0.25mm apertures (60 mesh) sieve, load port grinding bottle after fully mixing
In it is spare；
（2）Extraction concentration：Accurately weigh 20g（It is accurate to 0.01g）Sample grind fodder into 100 mL homogeneous cups, adds 40
2 min of mL trifluoroacetic acid aqueous solutions homogeneous, mixture is transferred in funnel and is filtered, and takes 10 mL of filtrate nitrogen in test tube to be blown to dry to the greatest extent,
It is to be clean to add 1mL n-hexanes；
（3）Column purification：Fu Luoli diatomite SPE pillars add the anhydrous Na of 2 cm height2SO4, with 3 mL n-hexanes-acetone soln
Activation, the wherein volume ratio of n-hexane and acetone are 10: 1；By step（2）Concentrate be transferred to pillar, then use 2mL every time
2 ~ 3 washing nitrogen blowpipes of n-hexane-acetone soln, and cleaning solution is moved into column；Eluted with 8 mL n-hexanes-acetone soln,
Filtrate nitrogen is blown to dry to the greatest extent, and n-hexane is settled to 1 mL, crosses 0.22 μm of pin type nylon leaching film in chromatography column feed materials bottle, to be determined.
Wherein, the detection comprises the concrete steps that：Solution to be measured is carried out using gas chromatography tandem mass spectrometry method in sample injection bottle
Measure；Wherein chromatographic condition is：Chromatographic column：Agilent122-5532UI DB-5MS（30m × 0.25mm, 0.25 μm, U.S.'s peace
Jie Lun companies）；Injector temperature：280℃；Carrier gas：High-pure helium, 1.0 mL/min of flow velocity；Splitless injecting samples；Sample size：1 μL；
Column oven heating schedule：70 DEG C of 1 min of holding of initial temperature, rise to 280 DEG C with 15 DEG C/min, keep 2 min；Wherein mass spectrum bar
Part is：Ionization pattern：Electron bombardment（EI）, 70 eV；280 DEG C of transmission line temperature；Scan mode：More reaction detection pattern MRM；
Ion source temperature：230℃；Cycle period：24s；Chromatography peak width：0.8s；Collision gas：High pure nitrogen, flow are 1.5 mL/
min；Solvent delay：5min；Parent ion, daughter ion, collision energy and residence time parameter are shown in Table 1；
1 multiple-reaction monitoring pattern of table（MRM）Parameter
Note：A quota ions, the qualitative ions of b
It is an advantage of the invention that：1st, for feed substrate, organic solvent trifluoroacetic acid aqueous solution is taken as Extraction solvent, through overrich
Contracting, the pretreatment mode of the small column purifications of Fu Luoli diatomite SPE, easy to operate, extraction efficiency is high, process economy；2nd, using gas
Phase chromatography-tandem mass spectrometry measure, sample size is few, and test limit, sensitivity and precision are high；3rd, the universality of this method is strong, fits
For different types of Feed Sample, it disclosure satisfy that the remaining disposable Rapid Extraction of 5a,6,9,9a-hexahydro-6,9-methano-2,4 in a variety of Feed Samples, purification, divide
From and detection requirement.
Brief description of the drawings
Fig. 1 is the MRM chromatograms of sample solution in embodiment 1（1- α -5a,6,9,9a-hexahydro-6,9-methano-2,4；2- β -5a,6,9,9a-hexahydro-6,9-methano-2,4）；
Fig. 2 is the MRM mass spectrograms of sample solution in embodiment 1（1- α -5a,6,9,9a-hexahydro-6,9-methano-2,4；2- β -5a,6,9,9a-hexahydro-6,9-methano-2,4）.
Embodiment
With reference to the specific embodiment technical solution that the present invention is further explained.These embodiments are merely to illustrate this hair
It is bright rather than limit the scope of the invention.
Embodiment 1：Detection to the horizontal additive amount blank Feed Samples of 10 μ g/Kg
（1）Sample pre-treatments step：Take feed grinder to crush, cross 0.25mm apertures (60 mesh) sieve, load mill after fully mixing
It is spare in mouth bottle；Accurately weigh 20g（It is accurate to 0.01g）Sample grind fodder into 100 mL homogeneous cups, adds 10 μ g/Kg
The standard items of horizontal additive amount, add 40 mL trifluoroacetic acid aqueous solutions homogeneous, 2 min；Liquid is transferred in funnel and is filtered, takes filtrate
10 mL nitrogen in test tube be blown to it is dry to the greatest extent, add 1mL n-hexanes it is to be clean；SPE pillars add the anhydrous Na of 2 cm height2SO4, with 3
ML n-hexanes-acetone soln（Volume ratio is 10: 1, similarly hereinafter）Activation；Concentrate is transferred to pillar, then every time with 2mL just oneself
2 ~ 3 washing nitrogen blowpipes of alkane-acetone soln, and cleaning solution is moved into column, eluted with 8 mL n-hexanes-acetone soln, filtrate
Nitrogen is blown to dry to the greatest extent, and n-hexane is settled to 1 mL, and it is to be measured in chromatography column feed materials bottle to cross 0.22 μm of pin type nylon leaching film；
（2）The step of detection：Sample injection bottle solution is measured using gas chromatography tandem mass spectrometry method；Wherein chromatographic condition is：Chromatography
Column：Agilent122-5532UI DB-5MS（30m × 0.25mm, 0.25 μm, Agilent company of the U.S.）；Injector temperature：280
℃；Carrier gas：High-pure helium, 1.0 mL/min of flow velocity；Splitless injecting samples；Sample size：1 μL；Column oven heating schedule：Initial temperature
70 DEG C of 1 min of holding, rise to 280 DEG C with 15 DEG C/min, keep 2 min；Wherein Mass Spectrometry Conditions are：Ionization pattern：Electron bombardment
（EI）, 70 eV；280 DEG C of transmission line temperature；Scan mode：More reaction detection patterns（MRM）；Ion source temperature：230℃；Follow
The ring cycle：24s；Chromatography peak width：0.8s；Collision gas：High pure nitrogen, flow are 1.5 mL/min；Solvent delay：5min；
Parent ion, daughter ion, collision energy and residence time parameter are shown in Table 1.
Testing result：Sample extracts by organic solvent, concentrates, purify after enter gas chromatography tandem mass spectrometry detection
MRM chromatograms as shown in Figure 1, MRM mass spectrograms as shown in Fig. 2, two kinds of 5a,6,9,9a-hexahydro-6,9-methano-2,4 compounds can be efficiently separated, detection time
For 17 minutes.
Embodiment 2：
（1）Sample pre-treatments step：Accurately weigh 25 g（It is accurate to 0.01g）Sample grind fodder into 100 mL homogeneous cups,
Add 50 mL trifluoroacetic acid aqueous solutions homogeneous, 2 min；Liquid is transferred in funnel and is filtered, takes 10 mL of filtrate in 50 mL pear shape bottles
It is threaded to do to the greatest extent with Rotary Evaporators, it is to be clean adds 1mL n-hexanes；Fu Luoli diatomite SPE pillars add the anhydrous of 1 cm height
Na2SO4, with 2 mL n-hexanes-acetone soln（Volume ratio is 10: 1, similarly hereinafter）Activation；Concentrate is transferred to pillar, then every time
Nitrogen blowpipe is washed with 2mL n-hexanes-acetone soln 2 ~ 3 times, and cleaning solution is moved into column, it is molten with 10 mL n-hexanes-acetone
Liquid elutes, and filtrate is threaded to do to the greatest extent with Rotary Evaporators, and n-hexane is settled to 1 mL, crosses 0.22 μm of pin type nylon leaching film in chromatography
It is to be measured in sample injection bottle；
（2）The step of detection：Sample injection bottle solution is measured using gas chromatography tandem mass spectrometry method；Wherein chromatographic condition is：Chromatography
Column：Agilent122-5532UI DB-5MS（30m × 0.25mm, 0.25 μm, Agilent company of the U.S.）；Injector temperature：290
℃；Carrier gas：High-pure helium, 1.0 mL/min of flow velocity；Splitless injecting samples；Sample size：1.5μL；Column oven heating schedule：Initial temperature
70 DEG C of 1 min of holding, rise to 280 DEG C with 15 DEG C/min, keep 2 min；Wherein Mass Spectrometry Conditions are：Ionization pattern：Electron bombardment
（EI）, 70 eV；290 DEG C of transmission line temperature；Scan mode：More reaction detection patterns（MRM）；Ion source temperature：230℃；Follow
The ring cycle：24s;Chromatography peak width：0.8s；Collision gas：High pure nitrogen, flow are 1.5 mL/min；Solvent delay：8 min；
Parent ion, daughter ion, collision energy and residence time parameter are shown in Table 1.
Embodiment 3：Feed a part sample is detected
（1）Sample pre-treatments step：Take feed to be crushed with pulverizer, cross 0.25mm apertures (60 mesh) sieve, load after fully mixing
It is spare in port grinding bottle；Accurately weigh 30g（It is accurate to 0.01g）Sample grind fodder into 100 mL homogeneous cups, adds 60 mL
2 min of trifluoroacetic acid aqueous solution homogeneous；Liquid is transferred in funnel and is filtered, takes 10 mL of filtrate nitrogen in test tube to be blown to dry to the greatest extent, is added
2mL n-hexanes are to be clean；SPE pillars add the anhydrous Na of 2 cm height2SO4, with 3 mL n-hexanes-acetone soln（Volume ratio is 10
: 1, similarly hereinafter）Activation；Concentrate is transferred to pillar, then washs nitrogen blowpipe with 2mL n-hexanes-acetone soln 2 ~ 3 times every time, and
Cleaning solution is moved into column, is eluted with 12 mL n-hexanes-acetone soln, filtrate nitrogen is blown to dry to the greatest extent, and n-hexane is settled to 1 mL,
It is to be measured in chromatography column feed materials bottle to cross 0.22 μm of pin type nylon leaching film；
（2）The step of detection：Sample injection bottle solution is measured using gas chromatography tandem mass spectrometry method；Wherein chromatographic condition is：Chromatography
Column：Agilent122-5532UI DB-5MS（30m × 0.25mm, 0.25 μm, Agilent company of the U.S.）；Injector temperature：290
℃；Carrier gas：High-pure helium, 1.0 mL/min of flow velocity；Splitless injecting samples；Sample size：2 μL；Column oven heating schedule：Initial temperature
70 DEG C of 1 min of holding, rise to 280 DEG C with 15 DEG C/min, keep 2 min；Wherein Mass Spectrometry Conditions are：Ionization pattern：Electron bombardment
（EI）, 70 eV；280 DEG C of transmission line temperature；Scan mode：More reaction detection patterns（MRM）；Ion source temperature：230℃；Follow
The ring cycle：24s;Chromatography peak width：0.8s；Collision gas：High pure nitrogen, flow 1.5mL/min；Solvent delay：8min；It is female
Ion, daughter ion, collision energy and residence time parameter are shown in Table 1.
Standard curve：The influence for avoiding matrix effect from detecting 5a,6,9,9a-hexahydro-6,9-methano-2,4, standard curve is established using extraction standard solution；
The concentration of extraction standard solution is respectively 5,10,50,100,500,1000 μ g/L, six ranks；Surveyed according to above-mentioned instrumental method
It is fixed, using the mass concentration of 5a,6,9,9a-hexahydro-6,9-methano-2,4 as abscissa（X）, using the peak area of quota ion as ordinate（Y）Draw standard working curve,
Linear equation, the related coefficient of two kinds of compounds are as shown in table 2；Mixed mark solution is added in blank sample, with signal-to-noise ratio S/N >=3
Determine the detection limit of method, signal-to-noise ratio S/N >=10 determine method quantitative limit, the detection limit and quantitative limit difference of three kinds of compounds pair
For 1 μ g/Kg, 4 μ g/Kg.
The linear and related coefficient of 2 5a,6,9,9a-hexahydro-6,9-methano-2,4 compound of table
| Compound | Linear equation | Related coefficient |
| α -5a,6,9,9a-hexahydro-6,9-methano-2,4 | Y=107.21X-590.97 | 0.9997 |
| β -5a,6,9,9a-hexahydro-6,9-methano-2,4 | Y=42.58X-283.57 | 0.9996 |
Testing result：Part internal feed sample is measured using this method, it turns out that, do not detected in most of sample
5a,6,9,9a-hexahydro-6,9-methano-2,4, has a small amount of target compound but all below 4 μ g/Kg in few Feed Sample.
Three specific embodiments of the present invention are above are only, but the design concept of the present invention is not limited thereto, all utilizations
This design carries out unsubstantiality change to the present invention, should all belong to the behavior for invading the scope of the present invention.
Claims (3)
1. the method for 5a,6,9,9a-hexahydro-6,9-methano-2,4, this method include sample pre-treatments and detecting step in gas chromatography tandem mass spectrometry method measure feed；
It is characterized in that：The sample pre-treatments step is：A certain amount of sample is weighed, is tried by extraction of organic solvent trifluoroacetic acid aqueous solution
After 5a,6,9,9a-hexahydro-6,9-methano-2,4 in agent extraction sample, nitrogen evaporator concentration, carries out concentrate using Fu Luoli diatomite SPE solid-phase extraction columns net
Change；The detecting step is：Purified prepare liquid, is separated and detected using gas chromatography tandem mass spectrometry, more reaction detections
MRM patterns carry out qualitative and quantitative.
2. the method for 5a,6,9,9a-hexahydro-6,9-methano-2,4 in gas chromatography tandem mass spectrometry method measure feed as claimed in claim 1, it is characterized in that described
Sample pre-treatments comprise the concrete steps that：
（1）Prepare sample：Take feed to be crushed with pulverizer, cross 0.25mm aperture sieves, be fitted into after fully mixing spare in port grinding bottle；
（2）Extraction concentration：20g accurately is weighed, grinds fodder sample into 100 mL homogeneous cups, adds 40 mL trifluoroacetic acid aqueous solutions
2 min of homogeneous, mixture is transferred in funnel and is filtered, and takes 10 mL of filtrate nitrogen in test tube to be blown to dry to the greatest extent, add 1mL just oneself
Alkane is to be clean；
（3）Column purification：Fu Luoli diatomite SPE pillars add the anhydrous Na of 2 cm height2SO4, with 3 mL n-hexanes-acetone soln
Activation, the wherein volume ratio of n-hexane and acetone are 10: 1；By step（2）Concentrate be transferred to pillar, then use 2mL every time
2 ~ 3 washing nitrogen blowpipes of n-hexane-acetone soln, and cleaning solution is moved into column；Eluted with 8 mL n-hexanes-acetone soln,
Filtrate nitrogen is blown to dry to the greatest extent, and n-hexane is settled to 1 mL, crosses 0.22 μm of pin type nylon leaching film in chromatography column feed materials bottle, to be determined.
3. the method for 5a,6,9,9a-hexahydro-6,9-methano-2,4 in gas chromatography tandem mass spectrometry method measure feed as claimed in claim 1, it is characterized in that described
Detection comprises the concrete steps that：Solution to be measured is measured using gas chromatography tandem mass spectrometry method in sample injection bottle；Wherein chromatographic condition
For：Chromatographic column：Agilent122-5532UI DB-5MS（30m × 0.25mm, 0.25 μm, Agilent company of the U.S.）；Injection port
Temperature：280℃；Carrier gas：High-pure helium, 1.0 mL/min of flow velocity；Splitless injecting samples；Sample size：1 μL；Column oven heating schedule：
70 DEG C of 1 min of holding of initial temperature, rise to 280 DEG C with 15 DEG C/min, keep 2 min；Wherein Mass Spectrometry Conditions are：Ionization pattern：
Electron bombardment（EI）, 70 eV；280 DEG C of transmission line temperature；Scan mode：More reaction detection patterns（MRM）；Ion source temperature：
230℃；Cycle period：24s；Chromatography peak width：0.8s；Collision gas：High pure nitrogen, flow are 1.5 mL/min；Solvent prolongs
Late：5min；Parent ion, daughter ion, collision energy and residence time parameter are shown in Table 1；
1 multiple-reaction monitoring pattern of table（MRM）Parameter
Note：A quota ions, the qualitative ions of b.
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Application publication date: 20180515 |