CN110514766A - The measuring method of trichloromethyl pyridine in a kind of food - Google Patents
The measuring method of trichloromethyl pyridine in a kind of food Download PDFInfo
- Publication number
- CN110514766A CN110514766A CN201910856422.1A CN201910856422A CN110514766A CN 110514766 A CN110514766 A CN 110514766A CN 201910856422 A CN201910856422 A CN 201910856422A CN 110514766 A CN110514766 A CN 110514766A
- Authority
- CN
- China
- Prior art keywords
- standard
- solution
- sample
- carboxylic acid
- pyridine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
- G01N30/14—Preparation by elimination of some components
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N2030/022—Column chromatography characterised by the kind of separation mechanism
- G01N2030/025—Gas chromatography
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N2030/042—Standards
- G01N2030/045—Standards internal
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
- G01N2030/067—Preparation by reaction, e.g. derivatising the sample
Abstract
The invention discloses a kind of measuring methods of trichloromethyl pyridine in food, sample is extracted through acetonitrile, through primary secondary amine SiClx glue (PSA), octadecylsilane chemically bonded silica (C18), the dispersion purification of Graphon (GCB) matrix, scavenging solution is derivative through esterification, it is stripped again with ethyl acetate, gas chromatography-mass spectrum/mass spectrograph measurement and confirmation, inner mark method ration.The rate of recovery of the measuring method, the all technicals such as detection limit and precision meet the requirements, and it is good to be applied particularly to corn, wheat, sorghum, corn and the detection of quick-fried paddy, reproducibility, this measuring method is easy to operate, result is accurate, has directive significance in inspection and quarantining for import/export field.
Description
Technical field
The present invention relates to a kind of measuring methods of trichloromethyl pyridine in technical field of analytical chemistry more particularly to food.
Background technique
Trichloromethyl pyridine can be used as nitrogen oxidation inhibitor and soil nitrogenous fertilizer synergy due to having selectively active to nitrogen-fixing bacteria
Agent, commonly referred to as nitrogen pyrrole quinoline.The oxidation that ammonium ion in soil can be postponed when applying with urea element and one piece of nitrogenous fertilizer, is one
The important pesticide medicine intermediate of kind.It can degrade rapidly to 6- chloropyridine -2- carboxylic acid in plant, animal and soil, be to apply
With the unique significant chemical residue generated after nitrogen pyrrole quinoline.
Currently, the detection of trichloromethyl pyridine and its metabolin 6- chloropyridine -2- carboxylic acid is still in the plant-derived food in China
It is so a blank, therefore, is highly desirable to establish trichloromethyl pyridine residual in the suitable plant-derived food of inlet and outlet
The detection method of amount, it is ensured that the quality of agricultural product, it is whole to improve business administration and domestic testing agency's level.
Summary of the invention
In view of the problems of the existing technology, the purpose of the present invention is to provide a kind of surveys of trichloromethyl pyridine in food
Determine method, the measuring method is easy to operate, result is accurate, and the rate of recovery, and all technicals such as detection limit and precision accord with
It closes and requires, reproducibility is good.
To achieve the above object, technical scheme is as follows:
The measuring method of trichloromethyl pyridine in a kind of food, comprising the following steps:
1) preparation of blank sample extracting solution: using the sample carboxylic acid remained without trichloromethyl pyridine and 6- chloropyridine -2-,
It extracts, purification is configured to blank sample extracting solution after derivative；
2) preparation of standard solution:
The standard solution includes standard reserving solution, and intermediate standard stock solution and derivative hybrid standard use liquid；
10mg trichloromethyl pyridine and 6- chloropyridine -2- carboxylic acid standard substance are weighed respectively, are configured to 1000mg/ with methanol
The standard reserving solution of L；
Appropriate standard reserving solution is drawn respectively, and the intermediate standard stock solution of 40mg/L is configured to methanol dilution；
0.50mL trichloromethyl pyridine and 6- chloropyridine -2- carboxylic acid standard reserving solution are drawn respectively in colorimetric cylinder, are passed through
It is settled to 1.0mL with blank sample extracting solution after derivative in step 1), the derivative hybrid standard for being configured to 20mg/L makes
Use liquid；
3) preparation of inner mark solution:
10mg 2- pyridine carboxylic acid methyl esters is weighed, is dissolved and is transferred in 10mL volumetric flask with ethyl acetate, constant volume mixing is
Internal standard stock solution, the internal standard stock solution are diluted with ethyl acetate, are configured to the inner mark solution of 10mg/L；
4) matrix hybrid standard working solution: the derivative hybrid standard of certain volume is drawn using liquid, as needed with empty
White sample extracting solution is diluted to the extraction standard working solution for being applicable in concentration, matching while using；
5) measurement of standard working curve: drawing a certain amount of derivative hybrid standard and use liquid, 40 μ L inner mark solutions are added,
Step by step with blank sample extracting solution be diluted to 0.0mg/L, 0.025mg/L, 0.050mg/L, 0.10mg/L, 0.20mg/L and
The standard working solution of 0.40mg/L is configured to serial matrix hybrid standard working solution, for gas chromatography-mass spectrum after filtering
Combined instrument measurement, using the ratio of pesticide quota ion peak area and internal standard compound quota ion peak area as ordinate, pesticide standard
Concentration of polymer solution and the ratio of internal standard compound mass concentration are abscissa, draw standard curve；
6) gas chromatography-mass spectrum/mass spectroscopy: where chromatographic column is THERMOTR-35MS quartz capillary column；Chromatography
Column temperature are as follows: 70 DEG C of holding 1.5min then with 20 DEG C/min temperature programming to 180 DEG C, then with 5 DEG C/min are warming up to 210 DEG C,
280 DEG C are warming up to 25 DEG C/min again, keeps 5min；Carrier gas: helium, purity >=99.999%, flow velocity 1.2mL/min；Sample introduction
Mouth temperature: 250 DEG C；Sample volume: 1 μ L；
7) it according to the testing result of step 6), is calculated three in sample using inner mark method ration, and according to (1) formula and (2) formula
The content of chloromethylpyridine and 6- chloropyridine -2- carboxylic acid:
Standard curve calibration: byA and b are acquired, then
In formula:
As--- the peak area of trichloromethyl pyridine or 6- chloropyridine -2- carboxylic acid in standard solution；
A′is--- the peak area of internal standard 2- pyridine carboxylic acid methyl esters in standard solution；
cs--- the concentration of trichloromethyl pyridine or 6- chloropyridine -2- carboxylic acid, unit mg/L in standard solution；
c′is--- the concentration of internal standard 2- pyridine carboxylic acid methyl esters, unit mg/L in standard solution；
C --- trichloromethyl pyridine or 6- chloropyridine -2- carboxylic acid is dense in sample solution derived from standard operating curves
Degree, unit mg/L；
cis--- the concentration of internal standard 2- pyridine carboxylic acid methyl esters, unit mg/L in sample solution；
A --- the peak area of trichloromethyl pyridine or 6- chloropyridine formic acid in sample；
Ais--- the peak area of internal standard 2- pyridine carboxylic acid methyl esters in sample；
X --- trichloromethyl pyridine or 6- chloropyridine -2- carboxylic acid content, unit mg/kg in sample；
V --- the constant volume of final sample liquid, unit mL；
M --- sample size representated by final sample liquid, unit g.
Further, the extraction to corn is respectively included in the step 1), and in wheat, sorghum, corn, quick-fried paddy
The extraction of any one；Wherein to the extraction step of corn are as follows: weigh sample 10g into 50mL centrifuge tube, 10mL second is added
Nitrile, 0.1mL formic acid, vortex 1min are shaked in oscillator and are extracted 15min, 3g sodium chloride are added, then after shaking 5min, 4500r/
Min is centrifuged 5min, takes supernatant 4mL, to be clean；To the extraction step of any one in wheat, sorghum, corn, quick-fried paddy are as follows: claim
It taking sample 5g into 50mL centrifuge tube, adds 15g sea sand, be added 5mL water, concussion dispersion adds 10mL acetonitrile, 0.1mL formic acid,
Vortex 1min is shaked in oscillator and is extracted 15min, 3g sodium chloride is added, then after shaking 5min, and 4500r/min is centrifuged 5min, is taken
Supernatant 4mL, it is to be clean.
Further, the purifying step in the step 1) are as follows: 4mL sample liquid to be clean is added to and includes 50mg ethylenediamine-N-
Propyl silane SiClx glue (PSA), 100mg octadecylsilane chemically bonded silica (C18), 100mg Graphon (GCB), 200mg
MgSO410mL plastic centrifuge tube in, be vortexed and mix 1min, 4500r/min is centrifuged 5min, it is accurate draw 2mL scavenging solution in
It in 10mL test tube, is dried with nitrogen in 40 DEG C of water-baths, 1ml methanol concussion dissolved residue is rapidly added, wait derive.
Further, the derivative step in the step 1) are as follows: the purified methanol of 1mL is waited for into derivative solution, is placed in ice water
The 200 μ l concentrated sulfuric acids are slowly added in bath, at 55 DEG C, derivative 30min, 50 DEG C of water-baths are blown to about surplus 400ul, and 5ml is added to be saturated chlorine
Change sodium solution, concussion mixes, and is transferred to 50ml centrifuge tube A, washs derivative test tube with 5ml ethyl acetate, and be transferred to A centrifugation
Pipe, concussion are extracted, and pipette ethyl acetate layer in clean 50ml centrifuge tube B, water phase adds 3ml, 3ml ethyl acetate to extract two respectively again
It is secondary, merge organic phase in B centrifuge tube, then plus 2% metabisulfite solution of 2ml in B centrifuge tube wash organic phase, pipette ethyl acetate
Layer crosses anhydrous sodium sulfate in nitrogen flushing colorimetric cylinder, elutes anhydrous sodium sulfate with a small amount of ethyl acetate, collects whole filtrates, at 40 DEG C
Nitrogen flushing concentration, adds internal standard 40ul (4.13), is settled to 2ml with ethyl acetate, then plus anhydrous sodium sulfate water removal, cross 0.2 μm of micropore
Filter membrane, to gas chromatography-mass spectrum/mass spectroscopy analysis.
Further, the condition measurement sample and matrix hybrid standard working solution in the step 6), if test substance
Chromatographic peak retention time and extraction standard working solution retention time deviation within ± 2.5%；Qualitative ion pair it is opposite
Abundance is consistent with the relative abundance of extraction standard working solution of concentration comparable, and deviation is less than maximum allowable offset range, then may be used
It is determined as in sample that there are corresponding determinands.
Further, in the step 7), trichloromethyl pyridine, 6- chloropyridine -2- carboxylic acid reference retention time respectively about
For 7.32min, 7.97min.
Further, in the step 7), the quantitative limit of trichloromethyl pyridine and 6- Chloro-2-Pyridyle carboxylic acid, corn is
0.025mg/kg, wheat, sorghum, corn and quick-fried paddy are 0.05mg/kg.
The measuring method of trichloromethyl pyridine, sample are extracted through acetonitrile in food in the present invention, through ethylenediamine-N- propyl
Silanized silica gel (PSA), octadecylsilane chemically bonded silica (C18), the dispersion purification of Graphon (GCB) matrix, scavenging solution
It is derivative through esterification, then be stripped with ethyl acetate, gas chromatography-mass spectrum/mass spectrograph measurement and confirmation, inner mark method ration.It should
The rate of recovery of measuring method, detection limit and all technicals such as precision meet the requirements, and are applied particularly to corn, small
Wheat, sorghum, corn and the detection of quick-fried paddy, reproducibility is good, this measuring method is easy to operate, result is accurate, examines inspection in entry and exit
Epidemic disease field has directive significance.
Detailed description of the invention
Fig. 1 is trichloromethyl pyridine standard items full scan mass spectrogram of the present invention；
Fig. 2 is 6- Chloro-2-Pyridyle carboxylate methyl ester standard items full scan mass spectrogram of the present invention；
Fig. 3 is trichloromethyl pyridine of the present invention, 6- Chloro-2-Pyridyle carboxylate methyl ester and 2- pyridine carboxylic acid methyl esters (internal standard) standard
The MRM chromatogram of product；
Fig. 4 .1 is the working curve of corn matrix 6- Chloro-2-Pyridyle carboxylic acid of the present invention；
Fig. 4 .2 is the working curve of wheat matrix 6- Chloro-2-Pyridyle carboxylic acid of the present invention；
Fig. 4 .3 is the working curve of sorghum matrix 6- Chloro-2-Pyridyle carboxylic acid of the present invention；
Fig. 4 .4 is the working curve of corn-base 6- Chloro-2-Pyridyle carboxylic acid of the present invention；
Fig. 4 .5 is the working curve of the quick-fried paddy matrix 6- Chloro-2-Pyridyle carboxylic acid of the present invention；
Fig. 5 .1 is the working curve of corn matrix trichloromethyl pyridine of the present invention；
Fig. 5 .2 is the working curve of wheat matrix trichloromethyl pyridine of the present invention；
Fig. 5 .3 is the working curve of sorghum matrix trichloromethyl pyridine of the present invention；
Fig. 5 .4 is the working curve of corn-base trichloromethyl pyridine of the present invention；
Fig. 5 .5 is the working curve of the quick-fried paddy matrix trichloromethyl pyridine of the present invention；
Fig. 6 .1 is corn blank (trichloromethyl pyridine) MRM chromatogram of the present invention；
Fig. 6 .2 is corn mark-on (trichloromethyl pyridine 0.025mg/kg) MRM chromatogram of the present invention；
Fig. 6 .3 is corn blank of the present invention (6- Chloro-2-Pyridyle carboxylic acid) MRM chromatogram；
Fig. 6 .4 is corn mark-on of the present invention (6- Chloro-2-Pyridyle carboxylic acid 0.025mg/kg) MRM chromatogram；
Fig. 7 .1 is wheat blank (trichloromethyl pyridine) MRM chromatogram of the present invention；
Fig. 7 .2 is wheat mark-on (trichloromethyl pyridine 0.05mg/kg) MRM chromatogram of the present invention；
Fig. 7 .3 is wheat blank of the present invention (6- Chloro-2-Pyridyle carboxylic acid) MRM chromatogram；
Fig. 7 .4 is wheat mark-on of the present invention (6- Chloro-2-Pyridyle carboxylic acid 0.05mg/kg) MRM chromatogram；
Fig. 8 .1 is sorghum blank (trichloromethyl pyridine) MRM chromatogram of the present invention；
Fig. 8 .2 is sorghum mark-on (trichloromethyl pyridine 0.05mg/kg) MRM chromatogram of the present invention；
Fig. 8 .3 is sorghum blank of the present invention (6- Chloro-2-Pyridyle carboxylic acid) MRM chromatogram；
Fig. 8 .4 is sorghum mark-on of the present invention (6- Chloro-2-Pyridyle carboxylic acid 0.05mg/kg) MRM chromatogram；
Fig. 9 .1 is corn blank (trichloromethyl pyridine) MRM chromatogram of the present invention；
Fig. 9 .2 is corn mark-on (trichloromethyl pyridine 0.05mg/kg) MRM chromatogram of the present invention；
Fig. 9 .3 is corn blank of the present invention (6- Chloro-2-Pyridyle carboxylic acid) MRM chromatogram；
Fig. 9 .4 is corn mark-on of the present invention (6- Chloro-2-Pyridyle carboxylic acid 0.05mg/kg) MRM chromatogram；
Figure 10 .1 is quick-fried paddy blank (trichloromethyl pyridine) the MRM chromatogram of the present invention；
Figure 10 .2 is quick-fried paddy mark-on (trichloromethyl pyridine 0.05mg/kg) the MRM chromatogram of the present invention；
Figure 10 .3 is quick-fried paddy blank (6- Chloro-2-Pyridyle carboxylic acid) the MRM chromatogram of the present invention；
Figure 10 .4 is quick-fried paddy mark-on (6- Chloro-2-Pyridyle carboxylic acid 0.05mg/kg) the MRM chromatogram of the present invention.
Specific embodiment
In the description of present embodiment, the orientation of the instructions such as term " on ", "lower", "front", "rear", "left", "right" or
Positional relationship is to be based on the orientation or positional relationship shown in the drawings, it is only for convenient for the description present invention and simplify description,
Rather than the device or element of indication or suggestion meaning must have a particular orientation, be constructed and operated in a specific orientation, because
This is not considered as limiting the invention.In addition, term " first ", " second " are used for description purposes only, and should not be understood as
Specific indication or suggestion relative importance.
In order to which what is be more clear is illustrated the technical solution in the present invention, carried out in the form of specific embodiment below
Explanation.
Embodiment
The present embodiment is the content of trichloromethyl pyridine and 6- Chloro-2-Pyridyle carboxylic acid in measurement food.The original of measuring method
Reason be sample extracted through acetonitrile, through primary secondary amine SiClx glue (PSA), octadecylsilane chemically bonded silica (C18),
The dispersion purification of Graphon (GCB) matrix, scavenging solution is derivative through esterification, then is stripped with ethyl acetate, gas-chromatography-matter
Spectrum/mass spectrograph measurement and confirmation, inner mark method ration.The trichloromethyl pyrrole suitable for wheat, sorghum, corn, corn and quick-fried paddy
The measurement of the qualitative, quantitative of pyridine and its metabolin 6- chloropyridine -2- carboxylic acid.
Reagent in the present embodiment is that analysis is pure, water is level-one as defined in GB/T 6682-2008 in addition to special indicate
Water.
Material requested includes:
Acetonitrile: chromatographically pure；Ethyl acetate: chromatographically pure；Methanol: chromatographically pure；Sodium chloride；
Anhydrous magnesium sulfate: burning 4h through 650 DEG C, is stored in after being cooled to room temperature in drier spare in sealing container；
Anhydrous sodium sulfate: burning 4h through 650 DEG C, is stored in after being cooled to room temperature in drier spare in sealing container；
The concentrated sulfuric acid；Formic acid.
Solution is prepared: saturated sodium chloride solution: 36g sodium chloride is dissolved in 100mL water；2% metabisulfite solution: 2g sulfuric acid
Sodium is dissolved in 100mL water；
Standard substance: trichloromethyl pyridine (Nitrapyrin), CAS No:1929-82-4, molecular formula: C6H3Cl4N is pure
Degree >=99.4%；
6- chloropyridine -2- carboxylic acid (6-Chloro-2-pyridinecarboxylic Acid), CAS No:4684-94-0,
Molecular formula: C6H4ClNO2, purity >=99.0%；
2- pyridine carboxylic acid methyl esters (Methyl picolinate), CAS No:2459-07-6, chemical formula: C7H7NO2, purity
>=98.0%, internal standard compound.
The configuration of solution:
The preparation of blank sample extracting solution: it with the sample carboxylic acid remained without trichloromethyl pyridine and 6- chloropyridine -2-, mentions
It takes, purifies, be configured to blank sample extracting solution after derivative；
The preparation of standard solution:
The standard solution includes standard reserving solution, and intermediate standard stock solution and derivative hybrid standard use liquid；
10mg trichloromethyl pyridine and 6- chloropyridine -2- carboxylic acid standard substance are weighed respectively, are configured to 1000mg/ with methanol
The standard reserving solution of L；
Appropriate standard reserving solution is drawn respectively, and the intermediate standard stock solution of 40mg/L is configured to methanol dilution；
0.50mL trichloromethyl pyridine and 6- chloropyridine -2- carboxylic acid standard reserving solution are drawn respectively in colorimetric cylinder, are passed through
It is settled to 1.0mL with blank sample extracting solution after derivative, the derivative hybrid standard for being configured to 20mg/L uses liquid；
The preparation of inner mark solution:
10mg 2- pyridine carboxylic acid methyl esters is weighed, is dissolved and is transferred in 10mL volumetric flask with ethyl acetate, constant volume mixing is
Internal standard stock solution, the internal standard stock solution are diluted with ethyl acetate, are configured to the inner mark solution of 10mg/L；
Matrix hybrid standard working solution: the derivative hybrid standard of certain volume is drawn using liquid, uses blank as needed
Sample extracting solution is diluted to the extraction standard working solution for being applicable in concentration, matching while using.
Material includes: primary secondary amine SiClx glue (PSA): 40~60 μm；Octadecylsilane chemically bonded silica
(C18): 40~60 μm；Graphon (GCB): 40~120 μm；Miillpore filter: 13mm × 0.22 μm, organic phase.
Instrument and equipment includes: gas-chromatography-triple quadrupole bar mass spectrometer: being furnished with electron bombardment ionization source (EI)；Analysis
Balance: sensibility reciprocal is respectively 0.0001g and 0.01g；Centrifuge: revolving speed is not less than 4500r/min；Tissue mashing machine；Horizontal oscillations
Device；Swirl mixing device；Heated water bath shaking table；Nitrogen evaporator: controllable temperature.
Sample preparation and preservation: corn, quick-fried paddy take representative sample about 500g, are put into tissue mashing machine and smash to pieces, dress
Enter in polyethylene bottle or bag, seal and indicates label；Wheat, sorghum, corn take representative sample about 500g, make it after crushing
It can be all put into polyethylene bottle or bag by 425 μm of standard mesh screen, seal and indicate label；The preservation of sample: by sample
It is stored respectively according to test with spare, is saved under the conditions of -18 DEG C, in the operating process of sampling and sample preparation, sample should be prevented
It is contaminated or occurs the variation of residuals content.
Determination step in the present invention includes:
1) extraction of sample respectively includes the extraction to corn, and to any one in wheat, sorghum, corn, quick-fried paddy
The extraction of kind；
The extraction of corn: weighing sample 10g (being accurate to 0.01g) into 50mL centrifuge tube, and 10mL acetonitrile is added,
0.1mL formic acid, vortex 1min are shaked in oscillator and are extracted 15min, 3g sodium chloride are added, then after shaking 5min, 4500r/min
It is centrifuged 5min, takes supernatant 4mL, it is to be clean.
The extraction of wheat, sorghum, corn, quick-fried paddy: sample 5g (being accurate to 0.01g) is weighed into 50mL centrifuge tube, adds 15g
Sea sand, is added 5mL water, and concussion dispersion adds 10mL acetonitrile, 0.1mL formic acid, vortex 1min shakes extraction in oscillator
3g sodium chloride is added in 15min, then after shaking 5min, 4500r/min is centrifuged 5min, takes supernatant 4mL, to be clean.
Measuring method selection acetonitrile in the present invention extracts, and adds 0.1mL formic acid, it is therefore an objective under acid acetonitrile system, 6-
Chloro-2-Pyridyle carboxylic acid can be extracted well acetonitrile layer, and formic acid is not added when it is demonstrated experimentally that extracting, and 6- Chloro-2-Pyridyle carboxylic acid returns
Yield is very low.
2) it purifies
4mL sample liquid to be clean is added to and includes 50mg primary secondary amine SiClx glue (PSA), 100mg octadecyl
Silane group silica gel (C18), 100mg Graphon (GCB), 200mg MgSO410mL plastic centrifuge tube in, be vortexed mix
1min.4500r/min is centrifuged 5min, and accurate 2mL scavenging solution of drawing is dried with nitrogen, rapidly in 10mL test tube in 40 DEG C of water-baths
1ml methanol is added and shakes dissolved residue, wait derive.
After measuring method sample in the present invention is extracted with acetonitrile, some polarity and moderately polar impurity are also extracted to
In acetonitrile, such as vitamin, pigment, for the property of these impurity, selected primary secondary amine SiClx glue (PSA),
Octadecylsilane chemically bonded silica (C18) and Graphon (GCB) are adsorbent.Then their dosage is carried out excellent
Change, take 100 μ g/L standard solution 1.0ml, purified respectively with 50mg, 75mg, 100mg, 200mg adsorbent, parallel 6 times,
Take the average rate of recovery, the purification result of different amounts be compared, the final dosage for determining adsorbent be 50mg PSA,
100mgC18 and 100mg GCB.
3) derivative
The purified methanol of 1mL is waited for into derivative solution, is placed in ice-water bath and is slowly added to the 200 μ l concentrated sulfuric acids, at 55 DEG C,
Derivative 30min, 50 DEG C of water-baths are blown to about surplus 400ul.
Add 5ml saturated sodium chloride solution, concussion mixes, is transferred to 50ml centrifuge tube A, washs derivative with 5ml ethyl acetate
Test tube, and it is transferred to A centrifuge tube, concussion is extracted, and pipettes ethyl acetate layer in clean 50ml centrifuge tube B, water phase adds respectively again
3ml, 3ml ethyl acetate extract twice, merge organic phase in B centrifuge tube, then plus 2% metabisulfite solution of 2ml washed in B centrifuge tube
Organic phase is washed, ethyl acetate layer is pipetted, anhydrous sodium sulfate is crossed in nitrogen flushing colorimetric cylinder, elutes anhydrous slufuric acid with a small amount of ethyl acetate
Sodium collects whole filtrates, and nitrogen flushing is concentrated at 40 DEG C, adds inner mark solution 40ul, is settled to 2ml, then plus anhydrous sulphur with ethyl acetate
Sour sodium water removal, crosses 0.2 μm of miillpore filter, analyzes to GC-MS/MS.
Derivative condition is optimized in the present embodiment,
The determination of derivative time: the 200ng/mL6- chloropyridine -2- carboxylic acid solution 1mL for taking methanol to prepare, add 200 microlitres it is dense
Sulfuric acid, derivative time select 10min, 20min, 30min, 60min respectively, and measurement result is shown, derivative 10min, response is minimum,
20min is slightly increased, and is tended towards stability later.Therefore derivative selection of time 30min.
The determination of derivative temperature: the 200ng/mL6- chloropyridine -2- carboxylic acid solution 1mL for taking methanol to prepare, add 100 microlitres it is dense
Sulfuric acid, derivative time 30min, derivative temperature select respectively 30 DEG C, measurement result is shown, 55 DEG C tend towards stability.Therefore the derivative time
55 DEG C of selection.
The selection of concentrated sulfuric acid dosage: derivatization reaction in derivatization process, has selected 50 μ l, 100 μ l, 200 μ l, the 300 dense sulphur of μ l
Sour dosage, experimental result discovery, if derivatives product solution, adds the 100 μ l concentrated sulfuric acids, can both derive completely, conversion ratio is steady
It is fixed, but after adding sample substrate, add the 100 μ l concentrated sulfuric acids, since impurity also consumes sulfuric acid, cause derivative conversion ratio decline unstable,
Therefore, it when derivative, has selected to add the 200 μ l concentrated sulfuric acids.
Derivative 6- Chloro-2-Pyridyle carboxylate methyl ester optimization for extracting condition:
After derivative, methanol need to be dried up, then be stripped with ethyl acetate, otherwise methanol content is high in saturated sodium chloride solution,
Solubility of the derivative 6- Chloro-2-Pyridyle carboxylate methyl ester in water phase is increased, to be substantially reduced 6- Chloro-2-Pyridyle carboxylic acid first
The extraction efficiency of ester, experimental result are shown in Table 1.
Under 1 different condition of table, extraction efficiency compares
The experimental results showed that should dry up methanol as far as possible when being stripped after derivative, need to extract three times, 6- Chloro-2-Pyridyle carboxylic
The recycling of sour methyl esters can satisfy requirement.
The selection of derivative 6- Chloro-2-Pyridyle carboxylate methyl ester extraction agent:
N-hexane, ethyl acetate is selected to be stripped derivative 6- Chloro-2-Pyridyle carboxylate methyl ester respectively, experimental result
Show with n-hexane extraction, the rate of recovery of 6- Chloro-2-Pyridyle carboxylate methyl ester only has 60% or so, is extracted with ethyl acetate, 6-
The rate of recovery of Chloro-2-Pyridyle carboxylate methyl ester is greater than 90%.Therefore select ethyl acetate as derivatization reaction after, 6- Chloro-2-Pyridyle carboxylic
The extraction agent of sour methyl esters.
4) gas chromatography-mass spectrum/mass spectroscopy
Instrument reference conditions:
A) chromatographic column: THERMOTR-35MS quartz capillary column；30m × 0.25mm × 0.25 μm or suitable person；
B) chromatogram column temperature: 70 DEG C of holding 1.5min, then with 20 DEG C/min temperature programming to 180 DEG C, then with 5 DEG C/min
210 DEG C are warming up to, then is warming up to 280 DEG C with 25 DEG C/min, keeps 5min；
C) carrier gas: helium, purity >=99.999%, flow velocity 1.2mL/min；
D) injector temperature: 250 DEG C；
E) sample volume: 1 μ L；
F) input mode: Splitless injecting samples；
G) electron bombardment ionization source: 70eV；
H) ion source temperature: 230 DEG C；
I) transmission line temperature: 280 DEG C；
J) solvent delay: 3min；
The selection of chromatographic condition mainly includes the selection of chromatographic column and chromatogram column temperature condition, trichloromethyl pyridine and 6- chlorine
The interaction of the silicone hydroxyl in pyridine ring and chromatographic column filler in the molecular structure of pyridine-2-carboxylic acids, will lead to chromatographic peak
Hangover, 6- chloropyridine -2- carboxylic acid polarity is stronger, sensitive to light, heat, oxygen, oxidizable, is unfavorable for directly using gas-chromatography-matter
Spectrometer analysis, by esterification reaction of organic acid, 6- chloropyridine -2- carboxylic acid is derived, and generates 6- Chloro-2-Pyridyle carboxylate methyl ester, polarity drop
Low, stability improves, and behavior is effectively maintained on gas chromatographic column.In an experiment, selected DB-1701, DB-5MS,
Tetra- chromatographic columns of DB-INOVWAX and TR-35MS are tested respectively.Pass through experimental selection THERMOTR-35MS quartz capillary
Tubing string is separated, which is (35%- phenyl)-Polysiloxane Stationary Phases, trichloromethyl pyridine and the chloro- 2- of 6-
The peak type of pyridinecarboxylate is sharp, no hangover, and the sensitivity of 6- Chloro-2-Pyridyle carboxylate methyl ester has compared with first three chromatographic column
It is significant to improve.Determinand can be made to obtain extraordinary separation, and chromatographic column is moderate.
Using EI original, in the positive-ion mode, one is carried out to trichloromethyl pyridine and 6- Chloro-2-Pyridyle carboxylate methyl ester respectively
Grade mass spectral analysis (Q1 scanning), obtains parent ion peak, carries out second mass analysis (daughter ion scanning) to parent ion peak, obtains broken
Piece ion information thereby determines that quantitative, qualitative ion pair.
This method uses Timed choice ion pattern, due to only narrow at one of its corresponding retention time to ion scan
It is carried out in narrow region, therefore, in identical entire scanning process, can make more to obtain longer residence time to ion,
To improve sensitivity, and reduce interfering with each other between peak and peak as far as possible.
Using MRM type collection data, by optimizing collision energy, reach each ion pair preferably in response to being shown in Table 2.
2 retention time of table and multiple-reaction monitoring ion and collision energy
Obtain the standard items full scan mass spectrogram and trichloromethyl of trichloromethyl pyridine and 6- Chloro-2-Pyridyle carboxylate methyl ester
The MRM chromatogram of pyridine, 6- Chloro-2-Pyridyle carboxylate methyl ester and 2- pyridine carboxylic acid methyl esters (internal standard) standard items is referring to Fig. 1-3.
The measurement of standard working curve
A certain amount of derivative hybrid standard is drawn using liquid, 40 μ L inner mark solutions are added, use blank sample extracting solution step by step
It is diluted to the standard working solution of 0.0mg/L, 0.025mg/L, 0.050mg/L, 0.10mg/L, 0.20mg/L and 0.40mg/L,
Be configured to serial matrix hybrid standard working solution after filtering, measured for gas chromatograph-mass spectrometer (GC-MS), with pesticide it is quantitative from
The ratio of sub- peak area and internal standard compound quota ion peak area is ordinate, pesticide standard concentration of polymer solution and internal standard compound quality
The ratio of concentration is abscissa, according to being measured under GC-MS/MS experiment condition determined by measuring method of the present invention, is drawn
Standard curve, specifically referring to figure 4. shown in .1-5.5.The result shows that dense when trichloromethyl pyridine and 6- Chloro-2-Pyridyle carboxylic acid
Degree is linear significant within the scope of 0.025~0.40mg/L.
Lower limit of measurement: the quantitative limit of this method trichloromethyl pyridine and 6- Chloro-2-Pyridyle carboxylic acid: corn 0.025mg/
Kg, wheat, sorghum, corn and quick-fried paddy are 0.05mg/kg.
About qualitative and quantitative measurement:
Qualitative determination: sample and matrix hybrid standard working solution are measured according to above-mentioned condition, if the color of test substance
Spectral peak retention time and the retention time deviation of extraction standard working solution are within ± 2.5%；The relative abundance of qualitative ion pair
Consistent with the relative abundance of extraction standard working solution of concentration comparable, deviation is no more than range as defined in table 3, then can determine that as sample
There are corresponding determinands in product.
With respect to the maximum allowable offset of abundance of ions when table 3 is qualitative
| Relative ion abundance | > 50% | > 20% to 50% | > 10% to 20% | ≤ 10% |
| It allow relative deviation | ± 20% | ± 25% | ± 30% | ± 50% |
Quantitative determination: being quantitative determined in this method using internal standard calibration curve method, to reduce matrix to the shadow of quantitative determination
It rings, the quantitative standard curve that should be drawn using extraction standard working solution with standard curve, and guarantees to be measured in institute's sample
The response of object is within the range of linearity.The reference of trichloromethyl pyridine, 6- chloropyridine -2- carboxylic acid under above-mentioned chromatographic condition
Retention time respectively may be about 7.32min, 7.97min.Corresponding trichloromethyl pyridine, 6- Chloro-2-Pyridyle carboxylate methyl ester and 2-
The MRM chromatogram of pyridine carboxylic acid methyl esters (internal standard) standard items is referring to Fig. 3.
Matrix effect refers to that the total outflow component in sample analysis liquid in addition to analyte changes the response of analyte,
To influence the accuracy and reproducibility of quantitative analysis.Experiment discovery, measures trichloromethyl pyridine and 6- Chloro-2-Pyridyle carboxylic acid first
Ester present matrix enhancement effect, trichloromethyl pyridine matrix effect be about 28%, 6- Chloro-2-Pyridyle carboxylate methyl ester matrix effect about
It is 11%, this method takes derivatives object, matrix with standard curve, inner mark method ration, makes trichloromethyl pyridine and the chloro- 2- of 6-
The rate of recovery of pyridinecarboxylate is corrected well.
After sample measurement, according to testing result, calculated three in sample using inner mark method ration, and according to (1) formula and (2) formula
The content of chloromethylpyridine and 6- chloropyridine -2- carboxylic acid:
Standard curve calibration: byA and b are acquired, then
In formula:
As--- the peak area of trichloromethyl pyridine or 6- chloropyridine -2- carboxylic acid in standard solution；
A′is--- the peak area of internal standard 2- pyridine carboxylic acid methyl esters in standard solution；
cs--- the concentration of trichloromethyl pyridine or 6- chloropyridine -2- carboxylic acid, unit mg/L in standard solution；
c′is--- the concentration of internal standard 2- pyridine carboxylic acid methyl esters, unit mg/L in standard solution；
C --- trichloromethyl pyridine or 6- chloropyridine -2- carboxylic acid is dense in sample solution derived from standard operating curves
Degree, unit mg/L；
cis--- the concentration of internal standard 2- pyridine carboxylic acid methyl esters, unit mg/L in sample solution；
A --- the peak area of trichloromethyl pyridine or 6- chloropyridine formic acid in sample；
Ais--- the peak area of internal standard 2- pyridine carboxylic acid methyl esters in sample；
X --- trichloromethyl pyridine or 6- chloropyridine -2- carboxylic acid content, unit mg/kg in sample；
V --- the constant volume of final sample liquid, unit mL；
M --- sample size representated by final sample liquid, unit g.
Fig. 6 .1-10.4 is respectively trichloromethyl pyridine and 6- Chloro-2-Pyridyle carboxylic acid sample blank, sample in different samples
Add the MRM chromatogram of recycling.
Precision measurement is carried out to actual samples such as corn, wheat, sorghum, corn and quick-fried paddy respectively, and is carried out
The trichloromethyl pyridine and 6- Chloro-2-Pyridyle carboxylic acid of various concentration add recovery test, and precision and rate of recovery data are shown in Table 4.
Meanwhile this method is verified through five units, does three water to corn, wheat, sorghum, corn and quick-fried paddy
Flat addition recovery experiment, verification result are shown in Table 5.
By result as can be seen that the rate of recovery of the method for inspection of the present invention, all technicals such as detection limit and precision
It meets the requirements, method is applied to corn, wheat, sorghum, corn and the detection of quick-fried paddy, and reproducibility is good, and detection method has
Advantage easy to operate, as a result accurate, can be widely used in food inspection.
Finally, it will be appreciated that the principle that embodiment of above is intended to be merely illustrative of the present and the example that uses
Property embodiment, however the present invention is not limited thereto.For those of ordinary skills, do not depart from it is of the invention
In the case where principle and essence, various changes and modifications can be made therein, these variations and modifications are also considered as protection scope of the present invention.
Trichloromethyl pyridine and 6- Chloro-2-Pyridyle carboxylic acid TIANZHU XINGNAO Capsul and precision experiment result (n=6) in table Room 4
Trichloromethyl pyridine and 6- Chloro-2-Pyridyle carboxylic acid TIANZHU XINGNAO Capsul and precision experiment result summary sheet between table Room 5
Claims (7)
1. the measuring method of trichloromethyl pyridine in a kind of food, which comprises the following steps:
1) it the preparation of blank sample extracting solution: with the sample carboxylic acid remained without trichloromethyl pyridine and 6- chloropyridine -2-, mentions
It takes, purifies, be configured to blank sample extracting solution after derivative；
2) preparation of standard solution:
The standard solution includes standard reserving solution, and intermediate standard stock solution and derivative hybrid standard use liquid；
10mg trichloromethyl pyridine and 6- chloropyridine -2- carboxylic acid standard substance are weighed respectively, are configured to 1000mg/L's with methanol
The standard reserving solution；
Appropriate standard reserving solution is drawn respectively, and the intermediate standard stock solution of 40mg/L is configured to methanol dilution；
0.50mL trichloromethyl pyridine and 6- chloropyridine -2- carboxylic acid standard reserving solution are drawn respectively in colorimetric cylinder, by step
1) it is settled to 1.0mL with blank sample extracting solution after the derivative in, the derivative hybrid standard for being configured to 20mg/L uses liquid；
3) preparation of inner mark solution:
10mg2- pyridine carboxylic acid methyl esters is weighed, dissolved with ethyl acetate and is transferred in 10mL volumetric flask, it is internal standard that constant volume, which mixes,
Stock solution, the internal standard stock solution are diluted with ethyl acetate, are configured to the inner mark solution of 10mg/L；
4) matrix hybrid standard working solution: the derivative hybrid standard of certain volume is drawn using liquid, uses blank sample as needed
Product extracting solution is diluted to the extraction standard working solution for being applicable in concentration, matching while using；
5) it the measurement of standard working curve: draws a certain amount of derivative hybrid standard and uses liquid, 40 μ L inner mark solutions are added, step by step
0.0mg/L, 0.025mg/L, 0.050mg/L, 0.10mg/L, 0.20mg/L and 0.40mg/L are diluted to blank sample extracting solution
Standard working solution, be configured to serial matrix hybrid standard working solution after filtering, for gas chromatograph-mass spectrometer (GC-MS) survey
It is fixed, using the ratio of pesticide quota ion peak area and internal standard compound quota ion peak area as ordinate, pesticide standard solution quality
The ratio of concentration and internal standard compound mass concentration is abscissa, draws standard curve；
6) gas chromatography-mass spectrum/mass spectroscopy: where chromatographic column is THERMOTR-35MS quartz capillary column；Chromatographic column temperature
Degree are as follows: 70 DEG C of holding 1.5min then with 20 DEG C/min temperature programming to 180 DEG C, then with 5 DEG C/min are warming up to 210 DEG C, then with
25 DEG C/min is warming up to 280 DEG C, keeps 5min；Carrier gas: helium, purity >=99.999%, flow velocity 1.2mL/min；Injection port temperature
Degree: 250 DEG C；Sample volume: 1 μ L；
7) according to the testing result of step 6), three chloromethanes in sample are calculated using inner mark method ration, and according to (1) formula and (2) formula
The content of yl pyridines and 6- chloropyridine -2- carboxylic acid:
Standard curve calibration: byIt acquiresaWithb, then
(1)
(2)
In formula:
A s ——The peak area of trichloromethyl pyridine or 6- chloropyridine -2- carboxylic acid in standard solution；
A ' is ——The peak area of internal standard 2- pyridine carboxylic acid methyl esters in standard solution；
c s ——The concentration of trichloromethyl pyridine or 6- chloropyridine -2- carboxylic acid, unit mg/L in standard solution；
c ' is ——The concentration of internal standard 2- pyridine carboxylic acid methyl esters, unit mg/L in standard solution；
c——The concentration of trichloromethyl pyridine or 6- chloropyridine -2- carboxylic acid in sample solution derived from standard operating curves, it is single
Position is mg/L；
c is ——The concentration of internal standard 2- pyridine carboxylic acid methyl esters, unit mg/L in sample solution；
A——The peak area of trichloromethyl pyridine or 6- chloropyridine formic acid in sample；
A is ——The peak area of internal standard 2- pyridine carboxylic acid methyl esters in sample；
X——Trichloromethyl pyridine or 6- chloropyridine -2- carboxylic acid content, unit mg/kg in sample；
V——The constant volume of final sample liquid, unit mL；
m——Sample size representated by final sample liquid, unit g.
2. measuring method according to claim 1, which is characterized in that respectively include mentioning corn in the step 1)
It takes, and the extraction to any one in wheat, sorghum, corn, quick-fried paddy；Wherein to the extraction step of corn are as follows: weigh sample
10mL acetonitrile, 0.1mL formic acid is added into 50mL centrifuge tube in product 10g, and vortex 1min is shaked in oscillator and extracted 15min, adds
Enter 3g sodium chloride, then after shaking 5min, 4500r/min is centrifuged 5min, takes supernatant 4mL, to be clean；To wheat, sorghum, jade
The extraction step of any one in rice, quick-fried paddy are as follows: weigh sample 5g into 50mL centrifuge tube, add 15g sea sand, 5mL water, shake is added
Dispersion is swung, 10mL acetonitrile, 0.1mL formic acid are added, vortex 1min is shaked in oscillator and is extracted 15min, 3g sodium chloride is added,
After shaking 5min again, 4500r/min is centrifuged 5min, takes supernatant 4mL, to be clean.
3. measuring method according to claim 1, which is characterized in that the purifying step in the step 1) are as follows: wait for 4mL
Purification sample liquid, which is added to, includes 50mg primary secondary amine SiClx glue (PSA), 100mg octadecylsilane chemically bonded silica
(C18), it in the 10mL plastic centrifuge tube of 100mg Graphon (GCB), 200mgMgSO4, is vortexed and mixes 1min, 4500r/
Min is centrifuged 5min, and accurate 2mL scavenging solution of drawing is dried with nitrogen in 40 DEG C of water-baths in 10mL test tube, is rapidly added 1ml methanol
Dissolved residue is shaken, wait derive.
4. measuring method according to claim 1, which is characterized in that the derivative step in the step 1) are as follows: 1mL is net
Methanol after change waits for derivative solution, is placed in ice-water bath and is slowly added to the 200 μ l concentrated sulfuric acids, at 55 DEG C, derivative 30min, and 50 DEG C
Water-bath is blown to about surplus 400ul, adds 5ml saturated sodium chloride solution, and concussion mixes, and 50ml centrifuge tube A is transferred to, with 5ml acetic acid second
Ester washs derivative test tube, and is transferred to A centrifuge tube, and concussion is extracted, and pipettes ethyl acetate layer in clean 50ml centrifuge tube B, water phase
Again respectively plus 3ml, 3ml ethyl acetate extract twice, merge organic phase in B centrifuge tube, then plus 2ml2% metabisulfite solution in B from
Heart pipe washs organic phase, pipettes ethyl acetate layer, crosses anhydrous sodium sulfate in nitrogen flushing colorimetric cylinder, is eluted with a small amount of ethyl acetate anhydrous
Sodium sulphate collects whole filtrates, and nitrogen flushing is concentrated at 40 DEG C, adds internal standard 40ul(4.13), 2ml is settled to ethyl acetate, then plus
Anhydrous sodium sulfate water removal, crosses 0.2mm miillpore filter, to gas chromatography-mass spectrum/mass spectroscopy analysis.
5. measuring method according to claim 1, which is characterized in that condition measurement sample and matrix in the step 6)
Hybrid standard working solution, if the chromatographic peak retention time of test substance and the retention time deviation of extraction standard working solution exist
Within ± 2.5%；The relative abundance of qualitative ion pair is consistent with the relative abundance of extraction standard working solution of concentration comparable, deviation
It is less than maximum allowable offset range, then can determine that as there are corresponding determinands in sample.
6. measuring method according to claim 1, which is characterized in that in the step 7), trichloromethyl pyridine, 6- chlorine pyrrole
The reference retention time of pyridine -2- carboxylic acid respectively may be about 7.32min, 7.97min.
7. measuring method according to claim 1, which is characterized in that in the step 7), trichloromethyl pyridine and 6- are chloro-
The quantitative limit of 2-Pyridinecarboxylic Acid, corn 0.025mg/kg, wheat, sorghum, corn and quick-fried paddy are 0.05mg/kg.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910856422.1A CN110514766B (en) | 2019-09-11 | 2019-09-11 | Method for determining trichloromethylpyridine in food |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910856422.1A CN110514766B (en) | 2019-09-11 | 2019-09-11 | Method for determining trichloromethylpyridine in food |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110514766A true CN110514766A (en) | 2019-11-29 |
| CN110514766B CN110514766B (en) | 2022-03-01 |
Family
ID=68630613
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910856422.1A Active CN110514766B (en) | 2019-09-11 | 2019-09-11 | Method for determining trichloromethylpyridine in food |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110514766B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111879879A (en) * | 2020-08-25 | 2020-11-03 | 福建省中孚检测技术有限公司 | Method for detecting methamidophos and octachlorodipropyl ether in plant food |
| CN112098553A (en) * | 2020-09-11 | 2020-12-18 | 安徽中创食品检测有限公司 | Method for detecting capsaicin compounds in duck neck |
| CN113433227A (en) * | 2021-01-08 | 2021-09-24 | 广州海关技术中心 | Method for detecting 6-chloropicolinic acid in vegetables and fruits |
| CN114594178A (en) * | 2022-01-25 | 2022-06-07 | 贵州健安德科技有限公司 | Method for detecting 3-methylpyridine in 30% chlorantraniliprole suspending agent by using HPLC (high performance liquid chromatography) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1416419A (en) * | 2000-01-14 | 2003-05-07 | 美国陶氏益农公司 | 4-aminopicolinates and their use as herbicides |
-
2019
- 2019-09-11 CN CN201910856422.1A patent/CN110514766B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1416419A (en) * | 2000-01-14 | 2003-05-07 | 美国陶氏益农公司 | 4-aminopicolinates and their use as herbicides |
Non-Patent Citations (5)
| Title |
|---|
| DURVESH SAWAN等: "Multi pesticide residue analysis in tobacco by GCMS/MS using QuEChERS as an extraction method", 《HTTPS://WWW.SHIMADZU.COM/AN/SITES/SHIMADZU.COM.AN/FILES/PIM/PIM_DOCUMENT_FILE/APPLICATIONS/POSTERS/9883/IPO214056.PDF》 * |
| TODD VANNELLI等: "Oxidation of Nitrapyrin to 6-Chloropicolinic Acid by the Ammonia-Oxidizing Bacterium Nitrosomonas europaea", 《APPLIED AND ENVIRONMENTAL MICROBIOLOGY》 * |
| TODD VANNELLI等: "Reductive Dehalogenation of the Trichloromethyl Group of Nitrapyrin by the Ammonia-Oxidizing Bacterium Nitrosomonas europaea", 《APPLIED AND ENVIRONMENTAL MICROBIOLOGY》 * |
| YUTAKA IWATA等: "Analytical Met hod for Nitrapyrin and 6-Chloropicolinic Acid Residues in Strawberry Fruit and Soil", 《J. AGRIC. FOOD CHEM.》 * |
| 仇珍等: "稻米中6―氯吡啶羧酸残留量测定", 《辽宁师范大学学报(自然科学版)》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111879879A (en) * | 2020-08-25 | 2020-11-03 | 福建省中孚检测技术有限公司 | Method for detecting methamidophos and octachlorodipropyl ether in plant food |
| CN111879879B (en) * | 2020-08-25 | 2023-09-26 | 福建省中孚检测技术有限公司 | Method for detecting methamidophos and octachlorodipropyl ether in plant food |
| CN112098553A (en) * | 2020-09-11 | 2020-12-18 | 安徽中创食品检测有限公司 | Method for detecting capsaicin compounds in duck neck |
| CN113433227A (en) * | 2021-01-08 | 2021-09-24 | 广州海关技术中心 | Method for detecting 6-chloropicolinic acid in vegetables and fruits |
| CN114594178A (en) * | 2022-01-25 | 2022-06-07 | 贵州健安德科技有限公司 | Method for detecting 3-methylpyridine in 30% chlorantraniliprole suspending agent by using HPLC (high performance liquid chromatography) |
| CN114594178B (en) * | 2022-01-25 | 2024-04-02 | 贵州健安德科技有限公司 | Method for detecting 3-methylpyridine in 30% chlorantraniliprole suspending agent by utilizing HPLC |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110514766B (en) | 2022-03-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110514766A (en) | The measuring method of trichloromethyl pyridine in a kind of food | |
| Liu et al. | Rapid analysis of organochlorine and pyrethroid pesticides in tea samples by directly suspended droplet microextraction using a gas chromatography–electron capture detector | |
| CN108254481A (en) | A kind of method of multi-class drug and personal care articles and pesticide in quick detection water | |
| Vandemark et al. | Liquid-chromatographic procedure for tricyclic drugs and their metabolites in plasma. | |
| CN105651924B (en) | The detection method of hormone in blood | |
| CN105784894B (en) | Pesticide residue detection method for traditional Chinese medicine | |
| CN109738565A (en) | The method of compound is illegally added in a kind of measurement health food | |
| Chen et al. | Dynamic ultrasound-assisted extraction coupled on-line with solid support derivatization and high-performance liquid chromatography for the determination of formaldehyde in textiles | |
| Chen et al. | Rapid screening of haloacetamides in water using salt-assisted liquid–liquid extraction coupled injection-port silylation gas chromatography–mass spectrometry | |
| Li et al. | Multiple antibodied based immunoaffinity columns preparation for the simultaneous analysis of deoxynivalenol and T-2 toxin in cereals by liquid chromatography tandem mass spectrometry | |
| Takekawa et al. | Analysis of cyanide in blood by headspace solid-phase microextraction (SPME) and capillary gas chromatography | |
| CN105424855B (en) | The method of anthraquinone residual quantity in gaschromatographic mass spectrometry/mass spectroscopy tealeaves | |
| CN103926340B (en) | The assay method of Nitrofuran antibiotics in a kind of cosmetics | |
| CN107462650A (en) | The detection method of environmental hormone in human urine | |
| Chen et al. | Solid phase extraction based microfluidic chip coupled with mass spectrometry for rapid determination of aflatoxins in peanut oil | |
| Gong et al. | Miniaturized ionic liquid dispersive liquid–liquid microextraction in a coupled-syringe system combined with UV for extraction and determination of danazol in danazol capsule and mice serum | |
| Xu et al. | Spectrophotometric determination of paracetamol with microwave assisted alkaline hydrolysis | |
| Elkady et al. | Forced degradation study to develop and validate stability-indicating RP-LC method for the determination of ciclesonide in bulk drug and metered dose inhalers | |
| Erarpat et al. | Quadruple isotope dilution gas chromatography-mass spectrometry after simultaneous derivatization and spraying based fine droplet formation liquid phase microextraction method for the accurate and sensitive quantification of chloroquine phosphate in human serum, urine and saliva samples at trace levels | |
| CN106053634A (en) | Method for detecting N-dimethyl nitrosamine in cooked meat products | |
| CN109254087A (en) | A kind of HPLC detection method of lauryl sodium sulfate in Ezetimibe piece sample | |
| CN104280495A (en) | Method for detecting validamycin A in water and rice plants | |
| CN104502486B (en) | A kind of apply the method for methyl vanillin and ethyl vanillin in Headspace-solid phase microextraction technical measurement milk powder | |
| Yuan et al. | Versatile two-phase solvent system for alkaloid separation by high-speed counter-current chromatography | |
| CN102866226A (en) | Method for using pyrazosulfuron-ethyl molecularly imprinted polymer for analyzing sulfonylurea herbicide and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB03 | Change of inventor or designer information | ||
| CB03 | Change of inventor or designer information |
Inventor after: Li Li Inventor after: Li Heli Inventor after: Yang Yang Inventor after: Han Shihe Inventor after: Chen Jie Inventor after: Yin Yu Inventor before: Li Li Inventor before: Li Heli Inventor before: Yang Yang Inventor before: Han Shihe Inventor before: Chen Jie Inventor before: Yin Yu |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant |