CN107085049A - A kind of edible Practice for Pesticide Residue in Agricultural Products is non-target, the electronic method of multi objective, rapid detection - Google Patents
A kind of edible Practice for Pesticide Residue in Agricultural Products is non-target, the electronic method of multi objective, rapid detection Download PDFInfo
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- CN107085049A CN107085049A CN201710247479.2A CN201710247479A CN107085049A CN 107085049 A CN107085049 A CN 107085049A CN 201710247479 A CN201710247479 A CN 201710247479A CN 107085049 A CN107085049 A CN 107085049A
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- G—PHYSICS
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- 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
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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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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Abstract
The invention discloses a kind of edible Practice for Pesticide Residue in Agricultural Products is non-target, the electronic method of multi objective, rapid detection, step：First：Set up the one-level accurate mass mass spectrometric data storehouse and FI mass spectrometric data storehouse of more than 1200 kinds world's common pesticides；Two mass spectrometric data storehouses are used for examination and the confirmation of agricultural chemical compound, are that every kind of agricultural chemicals sets up itself exclusive electronic ID card, the conventional identification method for replacing agricultural chemicals material standard to make reference with electronic standard is realized；Second：Develop the intelligent examination software of high resolution mass spectrum residues of pesticides mass spectrum Auto-matching Qualitative Identification, in software program implanting apparatus, the comparison of high speed, high flux, high accuracy, high reliability, advanced IT application and the test sample of automation and agricultural chemicals mass spectral database will be realized；3rd：A sample preparation is realized, using two kinds of detection techniques while the Multiple Pesticides of rapid detection 1200.Edible Practice for Pesticide Residue in Agricultural Products multi objective, non-target, rapid detection are realized, detection efficiency is greatly improved.
Description
Technical field
A kind of method for detecting of edible Practice for Pesticide Residue in Agricultural Products of present invention design, is refered in particular to a kind of for multiple eating agricultural product
In 1200 Multiple Pesticides residual rapid detection simultaneously the electronic method of non-target detection.
Background technology
It is common early in the World Health Organization (WHO) in 1976, food and agricultural organization (FAO) and United Nations Environment Programme (UNEP)
Establish global environment detecting system/food item (Global Environment Monitoring System, GEMS/
Food), it is intended to grasp member state's food pollution situation, understand food contaminant intake, protect health, give a impetus to trade hair
Exhibition.Now, food security is all lifted the strategic position to national security by countries in the world.Pesticide Residue is food security mark
One of standard, is also international trade access threshold.Meanwhile, it is more and more that the requirement to residues of pesticides shows kind, limits the quantity more next
Stricter development trend, that is, the Pesticide Residue threshold more and more higher that international trade is set up.Present European Union has formulated
162248 MRL standards of 839 kinds of agricultural chemicals, the U.S. has formulated 39147 MRL standards of 351 kinds of agricultural chemicals, and Japan formulates
51600 multinomial MRL standards of 579 kinds of agricultural chemicals, China has issued 3650 MRL standards of 381 kinds of agricultural chemicals for 2014.At present, state
The uniform limit generally used on border is limited the quantity as 10 μ g/kg.Therefore, the quick agriculture of high flux is all called in food security and international trade
Medicine residue detection technology, this undoubtedly also provides opportunities and challenges to vast pesticide residue analysis worker.Current numerous
In Analytical Techniques of Pesticide Residues, hydrolysis and condensation is to realize the optimized analysis means that quick detection is remained high flux more.
Current pesticide residue analysis is more with gas-chromatography, liquid chromatogram, gas chromatography-mass spectrum and liquid phase chromatogram-mass spectrometry combination
Based on technology.These detection techniques all carry out qualitative firstly the need of standard sample of pesticide control.For example, the inspection to 100 kinds of agricultural chemicals
Survey is accomplished by preparing corresponding 100 kinds of standard sample of pesticide control, and the agricultural chemicals outside this 100 kinds can be all missed.It is residual in agricultural chemicals
In the real work for staying laboratory, most laboratories are all without hundreds of standard sample of pesticide are laid in, and its reason is agricultural chemicals mark
Quasi- product are not only expensive, and the term of validity only has 2,3 years, it is necessary to overlapping investment.The standing standard sample of pesticide of common laboratory is only
There are tens kinds, the pesticide species of its daily monitoring are also just only limited to this tens kinds, thereby result in food safety monitoring leak.
The present inventor team, based on two class high resolution mass spectrums, have developed up to 1200 kinds agricultural chemicals by concentrating on studies for many years
Accurate mass mass spectrometric data storehouse and residues of pesticides detection techniques method, realize and be not required to standard control, can be to agricultural production
The Multiple Pesticides of product 1200 are remained, while rapid detection is detected, meet Agricultural Products Pesticide Residues high flux quick detection
Urgent need.
The content of the invention
The present invention by research and develop high flux high-resolution gas-chromatography-quadrupole rod flight time mass spectrum (GC-Q-TOFMS) and
Liquid chromatogram-quadrupole time-of-flight mass spec-trometry (LC-Q-TOFMS) new technology, it is proposed that a kind of edible Practice for Pesticide Residue in Agricultural Products is more
Index, non-target, rapid detection electronic method.Comprise the following steps that：
First：Set up more than 1200 kinds world's common pesticides one-level accurate mass mass spectrometric data storehouse (TOFMS) and two grades
Fragment ion mass spectrometric data storehouse (QTOFMS)；Two mass spectrometric data storehouses are used for examination and the confirmation of agricultural chemical compound, are every kind of
Agricultural chemicals sets up itself exclusive electronic ID card, realizes the tradition for replacing agricultural chemicals material standard to make reference with electronic standard
Authentication method；
Second：Develop high resolution mass spectrum (LC-Q-TOFMS and GC-Q-TOFMS) residues of pesticides mass spectrum Auto-matching qualitative
The intelligent examination software of identification, in software program implanting apparatus, will realize at high speed (0.5 hour), high flux (1200 kinds with
On), high accuracy (0.0001m/z), high reliability (6 confirmation point more than), the test sample of advanced IT application and automation with
The comparison of agricultural chemicals mass spectral database.
3rd：A sample preparation is realized, using two kinds of detection techniques (GC-Q-TOFMS and LC-Q-TOFMS) while fast
Speed 1200 Multiple Pesticides of detecting, realize edible Practice for Pesticide Residue in Agricultural Products multi objective, non-target, rapid detection；The side of substantially increasing
Method efficiency.
Wherein, the step of realizing edible Practice for Pesticide Residue in Agricultural Products multi objective, non-target, rapid detection is as follows：
(1) sample preparation：Agricultural product are homogenized through acetate acetonitrile and extracted, after being dehydrated and centrifuging, concentrate, then are passed through
Carbon/NH2 column purifications, acetonitrile+toluene elution remains of pesticide, are made after concentrated, filtering and treat sample measuring liquid；
(2) chromatographic mass spectrometry is detected：Simultaneously using LC-Q-TOF/MS and GC-Q-TOFMS detection agricultural chemicals；
(3) high resolution mass spectrum (LC-Q-TOFMS and GC-Q-TOFMS) residues of pesticides mass spectrum Auto-matching Qualitative Identification intelligence
Examination：More than 500 kinds agricultural chemicals are entered by LC-Q-TOFMS one-level precise information storehouse and FI mass spectrometric data storehouse
Row examination and confirmation；Examination is carried out to 700 Multiple Pesticides and true by GC-Q-TOFMS one-level accurate mass mass spectrometric data storehouse
Card, realizes the electronization detection of two kinds of technologies.
Wherein, described agricultural chemicals one-level accurate mass mass spectrometric data storehouse and FI mass spectrometric data storehouse pass through as follows
Method is obtained：
(1) standard sample of pesticide is configured to 1-5mg/L standard liquid respectively, imposed a condition lower through liquid chromatogram-quadrupole
Bar-flight time mass spectrum (LC-Q-TOFMS) and gas-chromatography-quadrupole rod flight time mass spectrum (GC-Q-TOFMS) obtain one-level
The full modal data of pattern, determines the full modal data of every kind of standard liquid.
(2) LC-Q-TOFMS obtained in step (1) the full modal data of first class mode, respectively obtains the chemistry of every kind of agricultural chemicals
The information such as molecular formula, accurate molecular weight, retention time, parent ion；By these Data Enters databases data files, and with
Corresponding agricultural chemicals information is associated, and builds up LC-Q-TOFMS one-level accurate mass mass spectrometric data storehouse, for data retrieval analysis；
The parent ion of every kind of agricultural chemicals in data acquisition interface sequentially inputs database, under QTOFMS patterns, distinguishes every kind of agricultural chemicals
Under 8 collision energies, carry out the collection of fragment ion full scan mass spectrogram, it is verified after fragment ion full scan mass spectrogram lead
Enter in PCDL softwares, import Library Editor, and, build up LC-Q-TOFMS two grade associated with corresponding agricultural chemicals information
Fragment ion mass spectrometric data storehouse.
(3) GC-Q-TOFMS obtained in step (1) the full modal data of first class mode, respectively obtains the chemistry of every kind of agricultural chemicals
Molecular formula, retention time, fragment ion accurate mass number, abundance of ions ratio；Fragment ion full scan mass spectrogram is imported into PCDL
In software, and it is associated with corresponding agricultural chemicals information, GC-Q-TOFMS one-level accurate mass mass spectrometric datas storehouse is built up, for data
Retrieval analysis.
Wherein, the intelligent examination of the Auto-matching Qualitative Identification is realized as follows：
(1) LC-Q-TOFMS one-level accurate mass mass spectrometric data storehouse examination and FI mass spectrometric data storehouse are true
Card：The one-level accurate mass mass spectrometric data storehouse set up is called in qualitative software, and it is qualitative to Mass Spectrometer Method target compound
Retrieval.Search argument is：Retention time deviation is defined to ± 0.5min, and accurate mass deviation is defined to ± 10ppm, according to every kind of
The measured value and one of compound electronic ID card information (retention time, accurate mass number, IP and isotope abundance)
The deviation of theoretical value, provides the score value of retrieval matching in level accurate mass mass spectrometric data storehouse, retrieves matching score value>60 change
Compound, is doubtful detection compound；Under Targeted MS/MS drainage patterns, the parent ion of doubtful detection compound is inputted,
Retention time and optimal collision energy, will detect collection of illustrative plates and the collection of illustrative plates in FI mass spectrometric data storehouse, in mirror image bar
Electronic ID card information (second order mses figure) matching confirmation, its matching score value are carried out under part again>70, that is, confirm to detect the mesh
Mark compound.
(2) GC-Q-TOFMS one-level accurate mass mass spectrometric data storehouse examination and confirmation：Called in qualitative software built
Vertical one-level accurate mass mass spectrometric data storehouse, and to Mass Spectrometer Method target compound retrieval by header.Search argument is：Retention time
Deviation is defined to ± 0.15min, and accurate mass deviation is defined to ± 20ppm, (is protected according to every kind of compound electronic ID card information
Stay time, fragment ion accurate mass number, fragment ion abundance ratio) measured value and one-level accurate mass mass spectrometric data storehouse in manage
By the deviation of value, retrieval matching result is provided, at least three fragment ions, comprehensive score are detected>60, that is, confirm to detect the target
Compound.
Beneficial effects of the present invention：
1st, the accurate mass mass spectrometric data that 1200 Multiple Pesticides accurate masses can reach 0.0001m/z is innovatively established
Storehouse, includes LC-Q-TOFMS one-level accurate mass mass spectrometric data storehouse, FI mass spectrometric data storehouse and GC-Q-TOFMS
One-level accurate mass mass spectrometric data storehouse.
2nd, the exclusive electronic ID card information of every kind of agricultural chemicals itself is set up in the database of two kinds of technologies, with electronic standard
Substitution agricultural chemicals material standard makees the conventional identification method of reference, and the non-target agricultural chemicals for realize high accuracy, high efficiency, economizing on resources is residual
Stay detection.Realize and replace traditional agricultural chemicals material standard to do the authentication method of reference with electronic standard, realize non-target agricultural chemicals
The development that jumps of residue detection technology.
3rd, innovatively establish with compound mass spectrums such as high-resolution accurate mass number, IP and isotope abundances
Information is criterion of identification, according to one-level accurate mass mass spectrometric data storehouse and FI mass spectrometric data storehouse to kind more than 500
The LC-Q-TOF/MS technical methods that agricultural chemicals is detected and confirmed；Creatively establish with fragment ion accurate mass number, broken
Piece abundance of ions than etc. compound Information in Mass Spectra for criterion of identification, according to one-level accurate mass mass spectrometric data storehouse to kind more than 700
The GC-Q-TOFMS technical methods that agricultural chemicals is detected and confirmed, two kinds of technologies revolutionize it is original using compound standard thing as
The qualitative model of reference, is that one kind does not need reference material control, quick, high flux, the accurately and reliably new skill of Detecting Pesticide
Art.Eliminate standard items and do reference, and with electronic standard Qualitative Identification, realize the biography that material standard is replaced with electronic ID card
System method, while also achieving the tech development from targeting detection to non-targeted examination.Resource is saved, pollution is reduced,
Analyze speed is improved, Green Development is fully meet, environment-friendly and clean and effective requirement.
4th, in LC-Q-TOFMS FI mass spectrometric data storehouse every kind of agricultural chemicals fragment ion full scan mass spectrogram
Information, is by preferred, obtained informative four differences of ion to full scan mass spectrogram under eight different collision energies
Fragment ion full scan figure under collision energy.
5th, the LC-Q-TOFMS residuals detection techniques method that the present invention is set up can according to target compound retention time,
The information such as accurate mass number, IP and isotope abundance, by with chemical combination in one-level accurate mass mass spectrometric data storehouse
The corresponding informance retrieval of thing is compared, and provides the matching degree score value of target compound.According to the score value of target compound, realize
Qualitative detecting to agricultural chemicals.
6th, the LC-Q-TOFMS residual detection techniques methods that the present invention is set up can be according to target compound fragment ion
Full scan mass spectrogram information, by believing with the full scan mass spectrogram of compound fragment ion in FI mass spectrometric data storehouse
Breath retrieval is compared, and provides the matching degree score value of target compound, realizes the qualitative confirmation to target compound.
7th, the GC-Q-TOFMS residuals detection techniques method that the present invention is set up can according to every kind of compound retention time,
The information such as fragment ion accurate mass number, fragment ion abundance ratio, by with compound in one-level accurate mass mass spectrometric data storehouse
Corresponding informance compare, provide retrieval matching result, according to fragment ion detection and scoring event, realize to target compound
Qualitative and confirmation.
8th, the Residual Pesticides in Farm Produce high flux sample preparation technology supporting with residual detection techniques method is developed.It is real
Show and only needed to a sample preparation, two kinds of technology difference sample detections, it is possible to the quick of the Multiple Pesticides of agricultural product 1200
Detecting and confirmation.
9th, in the 1200 kinds of agricultural chemicals detected at the same time, the agricultural chemicals detecting sensitivity more than 64.1% is micro- less than uniform limit 10
G kg, preferably meets the requirement of the horizontal examinations of various countries residues of pesticides MRL.
Brief description of the drawings
Fig. 1 LC-Q-TOFMS and GC-Q-TOFMS chemistry of pesticide polluter modal datas storehouse Establishing process
Fig. 2 residues of pesticides detecting flow process
Embodiment
The invention will be further described with specific embodiment below in conjunction with the accompanying drawings.
Fig. 1 is represented in LC-Q-TOFMS and GC-Q-TOFMS chemistry of pesticide polluter modal datas storehouse Establishing process, invention
Hold part to have described in detail.
Fig. 2 is represented in the electronic method of Pesticides Testing proposed by the present invention, once prepares sample, two kinds of technologies can be detected altogether
1200 Multiple Pesticides；Eliminate standard items and do reference, and with electronic standard Qualitative Identification, realize with electronic ID card for material object
The conventional method of standard, while also achieving the tech development from targeting detection to non-targeted examination.Resource is saved, is reduced
Pollution, improves analyze speed, fullys meet Green Development, environment-friendly and clean and effective requirement.
Meanwhile, the intelligent examination software of residues of pesticides mass spectrum Auto-matching Qualitative Identification has been researched and developed, software program has been planted
Enter in instrument, so that it may the detection of direct Run sample test solution, compared with agricultural chemicals mass spectrometric data storehouse, realize the high speed of method
(0.5 hour), high flux (more than 500/700 kind), high accuracy (0.0001m/z), high reliability (more than 10 confirmation points), height
Degree is information-based and automates, and also achieves electronization, substantially increases method efficiency.
Embodiment
Detect territorial scope：More than 600 sampled point of national 31 provincial capital/municipalities directly under the Central Government (284 districts), covers sample
The living area of national 25% population is covered, it is representative.
Detect sample type scope：18 146 kinds of class fruit and vegetables cover the 80% of national standard register, have shown method
General applicability.
The national various fruits vegetables of 18 class 140 sampling detail list
The sample of table 1 is classified and quantity (LC-Q-TOFMS detectings)
The sample of table 2 is classified and quantity (GC-Q-TOFMS detectings)
Embodiment 1
(specific pesticide variety refers to Publication No. CN105738460A, CN105628839A to 1200 Multiple Pesticides in celery
Listed agricultural chemicals in two patents) LC-Q-TOF/MS and GC-Q-TOF/MS detectings and confirmation technology embodiment, including it is as follows
Step；
1st, the specific steps of Sample Pretreatment Technique：
1.1 celery samples take edible part to shred, and mix, and mark is indicated in sealing；
1.2 weigh 10g celeries sample (being accurate to 0.01g), in 80mL centrifuge tubes, add the acetate acetonitriles of 40mL 1%,
With high-speed homogenization machine 13500r/min, 1min is extracted in homogenate, adds 1g sodium chloride, and 4g anhydrous magnesium sulfates vibrate 5min,
5min is centrifuged under 4200r/min, supernatant 20mL is taken, rotary evaporation is concentrated into about 1mL in 40 DEG C of water-baths, to be clean.
1.3 add the high anhydrous sodium sulfates of about 2cm in Carbon/NH2 posts.First drenched with 4mL acetonitriles+toluene (3+1, v/v)
SPE posts are washed, and discard efflux, when liquid level reaches the top of sodium sulphate, sample concentration liquid is transferred in SPE posts rapidly,
Under connect new heart bottle and receive.Wash sample liquid bottle three times with 2mL acetonitriles+toluene (3+1, v/v) every time again, and cleaning solution is moved into
In SPE posts.50mL liquid reservoirs are connected on post, agricultural chemicals and related chemicals are eluted with 25mL acetonitriles+toluene (3+1, v/v), are closed
And in heart bottle, and in 40 DEG C of water-baths spin concentration to about 0.5mL.
Concentrate is placed in drying under nitrogen by 1.4, adds 2mL acetonitrile+toluene (3+1, v/v), and ultrasound, which is redissolved, simultaneously to be mixed,
Two parts are divided into, is dried up under nitrogen.Use the formic acid acetonitriles of 1mL 1%+water (2+8, v/v) and 1mL n-hexane constant volumes, warp respectively again
After 0.22 μm of membrane filtration, detected respectively for LC-Q-TOF/MS and GC-Q-TOF/MS.
2nd, LC-Q-TOF/MS and GC-Q-TOF/MS operating conditions
LC-Q-TOF/MS operating conditions
Chromatographic condition：Liquid chromatogram mobile phase A is the 5mM formic acid of ammonium acetate -0.1%-water；Mobile phase B is acetonitrile；Gradient
Elution program is：0min：1%B, 3min：30%B, 6min：40%B, 9min：40%B, 15min：60%B, 19min：90%
B, 23min：90%B, 23.01min：1%B, runs 4min afterwards；Flow velocity is 0.4mL/min；Column temperature：40℃；Sample size：10μL.
Mass Spectrometry Conditions：Agilent6530LC-Q-TOF/MS capillary voltage：4000V；Dry temperature degree：325℃；It is dry
Pathogenic dryness flow 10L/min, sheath stream gas velocity 11L/min, sheath stream temperature degree are 325 DEG C；Atomization gas pressure 40psi, taper hole voltage
60V, fragmentation voltage 140V.Full scan karyoplasmic ratio scope is 50-1600m/z, and using internal standard reference solution to instrument quality essence
Degree carries out real time correction.It is right by Agilent MassHunter Workstation Software (versionB.05.00)
Mass Spectrometer Method results acquisition and processing.
GC-Q-TOF/MS operating conditions
Chromatographic condition：Gas chromatographic column is VF-1701ms, 30m × 0.25mm × 0.25 μm mass spectrum dedicated columns.Temperature programming
Process：40 DEG C keep 1min, then with 30 DEG C/min temperature programmings to 130 DEG C, then are warming up to 250 DEG C with 5 DEG C/min, then with 10
DEG C/min is warming up to 300 DEG C, keeps 5min；Carrier gas：Helium, purity >=99.999%, flow velocity 1.2mL/min；Injector temperature：
290℃；Sample size：1μL；Input mode：Splitless injecting samples.
Mass Spectrometry Conditions：EI sources voltage：70eV；Ion source temperature：230℃；GC-MS interface temperatures：280℃；Solvent delay：
6min.Mass scan range 50-600m/z, acquisition rate 2spectrum/s；Heptachlor epoxide is used to adjust retention time；Pass through
Agilent MassHunter Workstation Software (versionB.07.00) are gathered with locating to mass spectrum testing result
Reason.
3rd, celery Pesticide Residues are detected
3.1 under full scan pattern determination sample solution, detecting result is compared with TOF data storehouse, one-level is drawn
TOF scores.
3.2 meet desired compound for score, and two grades of acquisition methods are set up in software.
3.3 under MS/MS patterns, rerun sample solution, sample fragment ion full scan data are obtained, by itself and two
Fragment ion information is compared in level mass spectrum picture library, obtains two grades of QTOF scores.
4th, LC-Q-TOF/MS and GC-Q-TOF/MS detecting results in certain provincial capital's celery sample
16, the commercially available celery sample of certain provincial capital is gathered, is carried out using LC-Q-TOF/MS and GC-Q-TOF/MS technologies
1200 Multiple Pesticides residual detecting, LC-Q-TOF/MS detects 40 kinds of residues of pesticides with GC-Q-TOF/MS technologies, altogether 94 frequency,
It is related to 16, sample, concrete outcome is shown in Table 1.
LC-Q-TOF/MS and GC-Q-TOF/MS detecting results in the somewhere celery sample of table 1
Embodiment 2
1200 Multiple Pesticides (agricultural chemicals as indicated above) LC-Q-TOF/MS and GC-Q-TOF/MS is detected and true in tomato
Card technology embodiment.
Sample pre-treatments step, LC-Q-TOF/MS and GC-Q-TOF/MS operating conditions and sample Pesticide Residues were detected
Cheng Jun is with reference to embodiment 1.
LC-Q-TOF/MS and GC-Q-TOF/MS detecting results in certain provincial capital's tomato sample：Gather certain city of provincial capital
19, tomato sample is sold, carrying out 1200 Multiple Pesticides residual using LC-Q-TOF/MS and GC-Q-TOF/MS technologies detects, LC-Q-
TOF/MS detects 37 kinds of residues of pesticides with GC-Q-TOF/MS technologies, and 141 frequency, is related to 19, sample, concrete outcome is shown in Table altogether
2。
LC-Q-TOF/MS and GC-Q-TOF/MS detecting results in the somewhere tomato sample of table 2
Embodiment 3
1200 Multiple Pesticides (agricultural chemicals as indicated above) LC-Q-TOF/MS and GC-Q-TOF/MS is detected and true in grape
Card technology embodiment.
Sample pre-treatments step, LC-Q-TOF/MS and GC-Q-TOF/MS operating conditions and sample Pesticide Residues were detected
Cheng Jun is with reference to embodiment 1.
LC-Q-TOF/MS and GC-Q-TOF/MS detecting results in certain provincial capital's grape sample：Gather certain city of provincial capital
Grape sample 17 is sold, carrying out 1200 Multiple Pesticides residual using LC-Q-TOF/MS and GC-Q-TOF/MS technologies detects, LC-Q-
TOF/MS detects 39 kinds of residues of pesticides with GC-Q-TOF/MS technologies, and 147 frequency, is related to 16, sample, concrete outcome is shown in Table altogether
3。
LC-Q-TOF/MS and GC-Q-TOF/MS detecting results in the somewhere grape sample of table 3
Embodiment 4
1200 Multiple Pesticides (agricultural chemicals as indicated above) LC-Q-TOF/MS and GC-Q-TOF/MS is detected and confirmed in pears
Technology embodiment.
Sample pre-treatments step, LC-Q-TOF/MS and GC-Q-TOF/MS operating conditions and sample Pesticide Residues were detected
Cheng Jun is with reference to embodiment 1.
LC-Q-TOF/MS and GC-Q-TOF/MS detecting results in certain provincial capital's pears sample：Gather certain provincial capital commercially available
11, pears sample, carries out 1200 Multiple Pesticides residual using LC-Q-TOF/MS and GC-Q-TOF/MS technologies and detects, LC-Q-TOF/
MS detects 27 kinds of residues of pesticides with GC-Q-TOF/MS technologies, and 87 frequency, is related to 11, sample, concrete outcome is shown in Table 4 altogether.
LC-Q-TOF/MS and GC-Q-TOF/MS detecting results in the somewhere pears sample of table 4
Those listed above is a series of to be described in detail only for feasibility embodiment of the invention specifically
Bright, they simultaneously are not used to limit the scope of the invention, all equivalent implementations made without departing from skill spirit of the present invention
Or change should be included in the scope of the protection.
Claims (13)
1. a kind of edible Practice for Pesticide Residue in Agricultural Products is non-target, the electronic method of multi objective, rapid detection, it is characterised in that bag
Include following steps：
First：Set up the one-level accurate mass mass spectrometric data storehouse TOFMS and secondary fragment of more than 1200 kinds world's common pesticides from
Sub- mass spectrometric data storehouse QTOFMS；Two mass spectrometric data storehouses are used for examination and the confirmation of agricultural chemical compound, are that every kind of agricultural chemicals is set up
One itself exclusive electronic ID card, realizes electronization detection；
Second：Using high resolution mass spectrum LC-Q-TOFMS and GC-Q-TOFMS residues of pesticides mass spectrum Auto-matching Qualitative Identification intelligence
Screening method, realizes the comparison of test sample and agricultural chemicals mass spectral database；
3rd：Sample preparation, using two kinds of detection technique GC-Q-TOFMS and LC-Q-TOFMS while rapid detection 1200
Multiple Pesticides.
2. a kind of edible Practice for Pesticide Residue in Agricultural Products according to claim 1 is non-target, multi objective, the electronization of rapid detection
Method, it is characterised in that agricultural chemicals one-level accurate mass mass spectrometric data storehouse and FI spectra count in the first step
Obtained by the following method according to storehouse：
(1) standard sample of pesticide is configured to 1-5mg/L standard liquid respectively, impose a condition it is lower through liquid chromatogram-quadrupole rod-fly
Row time mass spectrum LC-Q-TOFMS and gas-chromatography-quadrupole rod flight time mass spectrum GC-Q-TOFMS obtain first class mode and compose number entirely
According to the full modal data of the every kind of standard liquid of measure；
(2) LC-Q-TOFMS obtained in step (1) the full modal data of first class mode, respectively obtains the chemical molecular of every kind of agricultural chemicals
The information such as formula, accurate molecular weight, retention time, parent ion；By these Data Enters databases data files, and with it is corresponding
Agricultural chemicals information be associated, build up LC-Q-TOFMS one-level accurate mass mass spectrometric data storehouse, for data retrieval analysis；
The parent ion of every kind of agricultural chemicals in data acquisition interface sequentially inputs database, under QTOFMS patterns, to every kind of agricultural chemicals
Respectively under 8 collision energies, carry out the collection of fragment ion full scan mass spectrogram, it is verified after fragment ion full scan mass spectrum
Figure is associated with corresponding agricultural chemicals information, builds up LC-Q-TOFMS FI mass spectrometric data storehouse；
(3) GC-Q-TOFMS obtained in step (1) the full modal data of first class mode, respectively obtains the chemical molecular of every kind of agricultural chemicals
Formula, retention time, fragment ion accurate mass number, abundance of ions ratio；By fragment ion full scan mass spectrogram and corresponding agricultural chemicals
Information is associated, and builds up GC-Q-TOFMS one-level accurate mass mass spectrometric datas storehouse, for data retrieval analysis.
3. a kind of edible Practice for Pesticide Residue in Agricultural Products according to claim 2 is non-target, multi objective, the electronization of rapid detection
Method, it is characterised in that fragment ion full scan mass spectrogram and corresponding agricultural chemicals information after verified described in (2)
Associated implements what the Library Editor being introduced into PCDL softwares were realized.
4. a kind of edible Practice for Pesticide Residue in Agricultural Products according to claim 2 is non-target, multi objective, the electronization of rapid detection
Method, it is characterised in that being associated fragment ion full scan mass spectrogram and corresponding agricultural chemicals information described in (3)
Implement and be introduced into what is realized in PCDL softwares.
5. a kind of edible Practice for Pesticide Residue in Agricultural Products according to claim 1 is non-target, multi objective, the electronization of rapid detection
Method, it is characterised in that the realization of the intelligent examination of Auto-matching Qualitative Identification in the second step includes：(1)LC-Q-
TOFMS one-level accurate mass mass spectrometric data storehouse examination and FI mass spectrometric data storehouse confirmation；(2) GC-Q-TOFMS
The storehouse examination of one-level accurate mass mass spectrometric data and confirmation.
6. a kind of edible Practice for Pesticide Residue in Agricultural Products according to claim 5 is non-target, multi objective, the electronization of rapid detection
Method, it is characterised in that the one-level accurate mass mass spectrometric data storehouse examination of (1) LC-Q-TOFMS and FI matter
What modal data storehouse was confirmed implements：
The one-level accurate mass mass spectrometric data storehouse set up is called in qualitative software, and it is qualitative to Mass Spectrometer Method target compound
Retrieval；Search argument is：Retention time deviation is defined to ± 0.5min, and accurate mass deviation is defined to ± 10ppm, according to every kind of
The deviation of theoretical value in the measured value of compound electronic ID card information and one-level accurate mass mass spectrometric data storehouse, provides retrieval
The score value matched somebody with somebody, retrieves matching score value>M compound, is doubtful detection compound；In Targeted MS/MS drainage patterns
Under, input the parent ion of doubtful detection compound, retention time and optimal collision energy, will detection collection of illustrative plates and secondary fragment from
Collection of illustrative plates in sub- mass spectrometric data storehouse, carries out electronic ID card information matches confirmation again under conditions mirror, its matching score value>
N, that is, confirm to detect the target compound.
7. a kind of edible Practice for Pesticide Residue in Agricultural Products according to claim 5 is non-target, multi objective, the electronization of rapid detection
Method, it is characterised in that the one-level accurate mass mass spectrometric data storehouse examination of (2) GC-Q-TOFMS and the specific reality of confirmation
It is existing：
The one-level accurate mass mass spectrometric data storehouse set up is called in qualitative software, and it is qualitative to Mass Spectrometer Method target compound
Retrieval, according to every kind of compound electronic ID card information measured value with one-level accurate mass mass spectrometric data storehouse theoretical value it is inclined
Difference, provides retrieval matching result, detects at least three fragment ions, comprehensive score>During P, that is, confirm to detect the target compound.
8. a kind of edible Practice for Pesticide Residue in Agricultural Products according to claim 6 is non-target, multi objective, the electronization of rapid detection
Method, it is characterised in that the electronic ID card information refers to：Retention time, accurate mass number, IP and isotope
Abundance.
9. a kind of edible Practice for Pesticide Residue in Agricultural Products according to claim 6 is non-target, multi objective, the electronization of rapid detection
Method, it is characterised in that the M is set to 60, and the N is set to 70.
10. a kind of edible Practice for Pesticide Residue in Agricultural Products according to claim 7 is non-target, multi objective, the electronics of rapid detection
Change method, it is characterised in that described electronic ID card information refers to：Retention time, fragment ion accurate mass number, fragment from
Sub- abundance ratio.
11. a kind of edible Practice for Pesticide Residue in Agricultural Products according to claim 7 is non-target, multi objective, the electronics of rapid detection
Change method, it is characterised in that the parameter of the retrieval is：Retention time deviation is defined to ± 0.15min, accurate mass deviation limit
It is set to ± 20ppm.
12. a kind of edible Practice for Pesticide Residue in Agricultural Products according to claim 7 is non-target, multi objective, the electronics of rapid detection
Change method, it is characterised in that the P is set to 60.
13. a kind of edible Practice for Pesticide Residue in Agricultural Products according to claim 1 is non-target, multi objective, the electronics of rapid detection
Change method, it is characterised in that the 3rd step is implemented：
(1) sample preparation：Agricultural product are homogenized through acetate acetonitrile and extracted, after being dehydrated and centrifuging, concentrate, then through carbon/NH2
Column purification, acetonitrile+toluene elution remains of pesticide, is made after concentrated, filtering and treats sample measuring liquid；
(2) chromatographic mass spectrometry is detected：Simultaneously using LC-Q-TOFMS and GC-Q-TOFMS detection agricultural chemicals；
(3) high resolution mass spectrum LC-Q-TOFMS and the intelligent examination of GC-Q-TOFMS residues of pesticides mass spectrum Auto-matchings Qualitative Identification：
Examination is carried out to more than 500 kinds agricultural chemicals by LC-Q-TOFMS one-level precise information storehouse and FI mass spectrometric data storehouse
And confirmation；Examination and confirmation are carried out to 700 Multiple Pesticides by GC-Q-TOFMS one-level accurate mass mass spectrometric data storehouse, realized
The electronization detection of two kinds of technologies.
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| CN201710247479.2A CN107085049A (en) | 2017-04-17 | 2017-04-17 | A kind of edible Practice for Pesticide Residue in Agricultural Products is non-target, the electronic method of multi objective, rapid detection |
| CN201810337240.9A CN108760909A (en) | 2017-04-17 | 2018-04-16 | A kind of edible Practice for Pesticide Residue in Agricultural Products is non-target, multi objective, rapid detection electronic method |
| PCT/CN2018/083341 WO2018192483A1 (en) | 2017-04-17 | 2018-04-17 | Electronic method for non-targeted, multi-index and rapid detection of pesticide residue in edible agricultural products |
| CN201811376380.3A CN109917028B (en) | 2017-04-17 | 2018-11-19 | The method for building up and detection method of agricultural chemical compound electronic identity database in edible agricultural product based on LC-Q-Orbitrap |
| CN201811376107.0A CN109557197B (en) | 2017-04-17 | 2018-11-19 | The method for building up and detection method of agricultural chemical compound electronic identity database in edible agricultural product based on GC-Q-Orbitrap |
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