CN108226341A - The accurate detecting method of Residual Pesticides in Farm Produce - Google Patents
The accurate detecting method of Residual Pesticides in Farm Produce Download PDFInfo
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Abstract
The invention discloses a kind of accurate detecting methods of Residual Pesticides in Farm Produce, are made of following step：(1) agricultural product with refiner are homogenized, add in water and acetonitrile is disperseed；(2) input magnetic Nano material carries out continuous concussion extraction；(3) magnetic Nano material for extracting absorption pesticide is detached from agricultural product solution using magnet；(4) magnetic Nano material for being adsorbed with pesticide is eluted using organic reagent, nitrogen blows concentration, and filtering obtains prepare liquid；(5) analysis detection is carried out to prepare liquid using ultra performance liquid chromatography triple quadrupole rods tandem mass spectrometry combined instruments.The accurate detecting method of Residual Pesticides in Farm Produce of the present invention has the advantages of operating time is short, and organic reagent consumption is few, and analysis cost is low, and analysis result is accurate.
Description
Technical field
The present invention relates to detection technique field more particularly to a kind of accurate detecting methods of Residual Pesticides in Farm Produce.
Background technology
In China, the Detecting Pesticide of agricultural product is typically all reference《The measure of persticide residue in fruits and vegetables
GB/T5009.218-2008》Or《500 kinds of pesticides and related chemicals residual in national food safety standard fruits and vegetables
The measure gas chromatography-mass spectrography GB 23200.8-2016 of amount》And《The measure gas of 51 kinds of pesticide multi-residues in veterinary antibiotics
Phase chromatography mass spectrometry NY/T 1380~2007》, on the one hand these reference standards are required for using very high organic of a large amount of purity
Reagent, and these reagents inevitably generate experimenter health hazard, on the other hand also need to using expensive
Various solid phase adsorption pillars, these reagents and pillar have to obtain after use appropriate processing again, it is generally time-consuming,
Arduously, and with high costs, main employed in continuous mode is all gas chromatography-mass spectrometry, the level four bars matter of single-stage
Spectrum rely solely on characteristic ion carry out it is qualitative, the knot of qualitative inaccuracy is susceptible in the relative complex food analysis of matrix
Fruit, so the accurate method of quick, economic, efficient, environmentally friendly and science and more accurate detection method must be developed to agricultural production
Pesticide residue in product carries out qualitative and quantitative detection.
Invention content
For the deficiencies in the prior art, ultra performance liquid chromatography-string is utilized the object of the present invention is to provide a kind of
Join triple level four bars mass spectrographs and accurately measure the remaining method of Multiple Pesticides in agricultural product.The technical issues of this method can solve
Be to provide it is a kind of it is more simple, accurate, greenly measure agricultural product in remains of pesticide method.
The technical problems to be solved by the invention are achieved by the following technical solution：
Accurate detecting method in Residual Pesticides in Farm Produce agricultural product of the present invention, is made of following step：
(1) agricultural product with refiner are homogenized, add in water and acetonitrile is disperseed；
(2) input magnetic Nano material carries out continuous concussion extraction；
(3) magnetic Nano material for extracting absorption pesticide is detached from agricultural product solution using magnet；
(4) magnetic Nano material for being adsorbed with pesticide is eluted using organic reagent, nitrogen blows concentration, and filtering obtains
Prepare liquid；
(5) analysis detection is carried out to prepare liquid using ultra performance liquid chromatography triple quadrupole rods tandem mass spectrometry combined instruments.
Specifically, the exact method that pesticide detects simultaneously in agricultural product of the present invention, is made of following step：
(1) 100~110g agricultural product with refiner are homogenized, obtain slurries；3~10g slurries are taken in 20~70mL
In tool plug centrifuge tube, 15~25mL deionized waters and 1~3mL acetonitriles are then added in, is shaken 2~5 minutes；
(2) 50~150mg magnetic Nano materials are added in into the tool plug centrifuge tube of step (1), continue 3~10 points of concussion
Clock；
(3) magnet is placed in centrifuge tube side wall, magnetic Nano material fully adsorbs the pesticide in agricultural product, has magnetism
Magnetic Nano material be attracted on the side wall by near magnet, discard the mixed liquor of agricultural product, acetonitrile and water, use deionized water
Magnetic Nano material is cleaned 2~3 times, discards cleaning solution；
(4) magnetic Nano material ultrasound in centrifuge tube is filled in tool using 2~5mL of organic solvent to elute 5~10 minutes, it is magnetic
The pesticide of nano-particle absorption is eluted in organic solvent, obtains eluent；Then nitrogen blow concentrate eluant to 0.8~
1.2mL, filtering, obtains prepare liquid；Wherein described organic solvent is acetonitrile and methanol with volume ratio (3~4)：The mixing of 1 composition
Solvent；
(5) machine on is analyzed prepare liquid using the triple quadrupole rods tandem mass spectrometry combined instruments of ultra performance liquid chromatography, is adopted
Qualitative, quantitative measure is carried out with external standard working curve method, obtains the accurate measurement result of Residual Pesticides in Farm Produce.
Preferably, the deionized water dosage for cleaning magnetic Nano material in step (3) every time is 2~5mL.
Preferably, magnetic Nano material described in step (2) is Fe3O4@SiO2@PDA state magnetic Nano material or
Fe3O4@SiO2The mesoporous SiO of@2@PDA state magnetic Nano material, and wherein PDA is poly-dopamine.
The Fe3O4@SiO2The specific building-up process of@PDA magnetic Nano materials is：
S1 is by FeCl3·6H2O is with ethylene glycol with solid-to-liquid ratio 1：(50~60) (g/mL) mix, magnetic agitation effect under with
200~300 revs/min are stirred 0.5~1 hour, then add in FeCl3·6H2The sodium acetate that 2.5~3 times of O weight, continue with
200~300 revs/min are stirred 0.5~1 hour, obtain mixed liquor；Mixed liquor is transferred to teflon lined stainless steel height
It presses in reaction kettle, is reacted 10~13 hours in 180~200 DEG C of heating；Reaction product is separated and collected outside plus under magnetic fields,
And with the washes of absolute alcohol of 40~60 times of reaction product weight, under conditions of 40~50 DEG C, 0.07~0.09MPa of vacuum degree
It is 6~10 hours dry, obtain black solid Fe3O4Nanoparticle；
S2 is by Fe3O4Nanoparticle is with solid-to-liquid ratio (2~3)：1 (mg/mL) is added to the hydrochloric acid of 1~2mol/L of molar concentration
In, it is ultrasonically treated 5~10 minutes under conditions of 200~500W of ultrasonic power, 25~35kHz of supersonic frequency, then uses Fe3O4
The deionized water that 80~200 times of nanoparticle weight is by Fe3O4Nanoparticle cleans up；Then by the Fe after cleaning3O4Nanometer
Microballoon adds in the mixed solution of the ethanol/water volume ratio 4/1 of 8~12 times of hydrochloric acid volume, adds 0.09~0.1 times of hydrochloric acid volume
Mass fraction 28% concentrated ammonia liquor, continue under conditions of 200~500W of ultrasonic power, 25~35kHz of supersonic frequency ultrasonic
Processing 10~30 minutes, obtains mixed liquor；Then, the positive esters of silicon acis of 0.04~0.05 times of hydrochloric acid volume is added in mixed liquor,
It is stirred to react 5~7 hours with 200~300 revs/min in 25~30 DEG C so that positive esters of silicon acis completes hydrolysis and polycondensation, collects anti-
Answer product；With 50~70 times of washes of absolute alcohol of reaction product weight, in 50~60 DEG C, 0.07~0.09MPa of vacuum degree
Under the conditions of dry 6~10 hours, obtain Fe3O4@SiO2Magnetic Nano microsphere；
S3 weighs dopamine hydrochloride and the Tris buffer solutions of molar concentration 10mM, with solid-to-liquid ratio 1：(0.8~1.2) (mg/
ML it) mixes；Then add in Fe3O4@SiO2Magnetic Nano microsphere, Fe3O4@SiO2The matter of magnetic Nano microsphere and dopamine hydrochloride
Amount is than being 1：(4~5) are stirred to react 16~20 hours in 20~30 DEG C with 200~300 revs/min；It, will be anti-after the completion of reaction
Liquid is answered to be centrifuged 10~15 minutes with 2000~3000 revs/min, collects bottom solid；By bottom solid bottom solid weight 50
After the deionized water washing of~70 times of 100~200 times of absolute ethyl alcohol and bottom solid weight, in 50~60 DEG C, vacuum degree
It is 6~10 hours dry under conditions of 0.07~0.09MPa, obtain the Fe3O4@SiO2@PDA magnetic Nano materials.
As the improved technical solution of the present invention, the Fe3O4@SiO2The specific building-up process of@PDA magnetic Nano materials
For：
S1 is by FeCl3·6H2O is with ethylene glycol with solid-to-liquid ratio 1：(50~60) (g/mL) mix, magnetic agitation effect under with
200~300 revs/min are stirred 0.5~1 hour, then add in FeCl3·6H2The sodium acetate that 2.5~3 times of O weight, continue with
200~300 revs/min are stirred 0.5~1 hour；Continuously add FeCl3·6H2The surfactant that 1.6~2 times of O weight, with
200~300 revs/min are stirred 15~25 minutes, obtain mixed liquor；Mixed liquor is transferred to teflon lined stainless steel height
It presses in reaction kettle, is reacted 10~13 hours in 180~200 DEG C of heating；Reaction product is separated and collected outside plus under magnetic fields,
And with the washes of absolute alcohol of 40~60 times of reaction product weight, under conditions of 40~50 DEG C, 0.07~0.09MPa of vacuum degree
It is 6~10 hours dry, obtain black solid Fe3O4Nanoparticle；
S2 is by Fe3O4Nanoparticle is with solid-to-liquid ratio (2~3)：1 (mg/mL) is added to the hydrochloric acid of 1~2mol/L of molar concentration
In, it is ultrasonically treated 5~10 minutes under conditions of 200~500W of ultrasonic power, 25~35kHz of supersonic frequency, then uses Fe3O4
The deionized water that 80~200 times of nanoparticle weight is by Fe3O4Nanoparticle cleans up；Then by the Fe after cleaning3O4Nanometer
Microballoon adds in the mixed solution of the ethanol/water volume ratio 4/1 of 8~12 times of hydrochloric acid volume, adds 0.09~0.1 times of hydrochloric acid volume
Mass fraction 28% concentrated ammonia liquor, continue under conditions of 200~500W of ultrasonic power, 25~35kHz of supersonic frequency ultrasonic
Processing 10~30 minutes, obtains mixed liquor；Then, the positive esters of silicon acis of 0.04~0.05 times of hydrochloric acid volume is added in mixed liquor,
It is stirred to react 5~7 hours with 200~300 revs/min in 25~30 DEG C so that positive esters of silicon acis completes hydrolysis and polycondensation, collects anti-
Answer product；With 50~70 times of washes of absolute alcohol of reaction product weight, in 50~60 DEG C, 0.07~0.09MPa of vacuum degree
Under the conditions of dry 6~10 hours, obtain Fe3O4@SiO2Magnetic Nano microsphere；
S3 weighs dopamine hydrochloride and the Tris buffer solutions of molar concentration 10mM, with solid-to-liquid ratio 1：(0.8~1.2) (mg/
ML it) mixes；Then add in Fe3O4@SiO2Magnetic Nano microsphere, Fe3O4@SiO2The matter of magnetic Nano microsphere and dopamine hydrochloride
Amount is than being 1：(4~5) are stirred to react 16~20 hours in 20~30 DEG C with 200~300 revs/min；It, will be anti-after the completion of reaction
Liquid is answered to be centrifuged 10~15 minutes with 2000~3000 revs/min, collects bottom solid；By bottom solid bottom solid weight 50
After the deionized water washing of~70 times of 100~200 times of absolute ethyl alcohol and bottom solid weight, in 50~60 DEG C, vacuum degree
It is 6~10 hours dry under conditions of 0.07~0.09MPa, obtain the Fe3O4@SiO2@PDA magnetic Nano materials.
It is further preferred that the Fe3O4@SiO2The mesoporous SiO of@2The specific building-up process of@PDA magnetic Nano materials is：
S1 is by FeCl3·6H2O is with ethylene glycol with solid-to-liquid ratio 1：(50~60) (g/mL) mix, magnetic agitation effect under with
200~300 revs/min are stirred 0.5~1 hour, then add in FeCl3·6H2The sodium acetate that 2.5~3 times of O weight, continue with
200~300 revs/min are stirred 0.5~1 hour；Continuously add FeCl3·6H2The surfactant that 1.6~2 times of O weight, with
200~300 revs/min are stirred 15~25 minutes, obtain mixed liquor；Mixed liquor is transferred to teflon lined stainless steel height
It presses in reaction kettle, is reacted 10~13 hours in 180~200 DEG C of heating；Reaction product is separated and collected outside plus under magnetic fields,
And with the washes of absolute alcohol of 40~60 times of reaction product weight, under conditions of 40~50 DEG C, 0.07~0.09MPa of vacuum degree
It is 6~10 hours dry, obtain black solid Fe3O4Nanoparticle；
S2 is by Fe3O4Nanoparticle is with solid-to-liquid ratio (2~3)：1 (mg/mL) is added to the hydrochloric acid of 1~2mol/L of molar concentration
In, it is ultrasonically treated 5~10 minutes under conditions of 200~500W of ultrasonic power, 25~35kHz of supersonic frequency, then uses Fe3O4
The deionized water that 80~200 times of nanoparticle weight is by Fe3O4Nanoparticle cleans up；Then by the Fe after cleaning3O4Nanometer
Microballoon adds in the mixed solution of the ethanol/water volume ratio 4/1 of 8~12 times of hydrochloric acid volume, adds 0.09~0.1 times of hydrochloric acid volume
Mass fraction 28% concentrated ammonia liquor, continue under conditions of 200~500W of ultrasonic power, 25~35kHz of supersonic frequency ultrasonic
Processing 10~30 minutes, obtains mixed liquor；Then, the positive esters of silicon acis of 0.04~0.05 times of hydrochloric acid volume is added in mixed liquor,
It is stirred to react 5~7 hours with 200~300 revs/min in 25~30 DEG C so that positive esters of silicon acis completes hydrolysis and polycondensation, collects anti-
Answer product；With 50~70 times of washes of absolute alcohol of reaction product weight, in 50~60 DEG C, 0.07~0.09MPa of vacuum degree
Under the conditions of dry 6~10 hours, obtain Fe3O4@SiO2Magnetic Nano microsphere；
S3 is by Fe3O4@SiO2Magnetic Nano microsphere, absolute ethyl alcohol and deionized water are with 1：(60~80)：80(g/mL/mL)
Mixing, is ultrasonically treated 15~20 minutes under conditions of 200~500W of ultrasonic power, 25~35kHz of supersonic frequency；Then add in
The mass fraction that 0.17~0.2 times of deionized water volume is 28% concentrated ammonia liquor and Fe3O4@SiO2Magnetic Nano microsphere weight 2~
3 times of cetyl trimethylammonium bromide is stirred 30~40 minutes with 200~300 revs/min；Continuously add ammonium hydroxide volume 0.4
~0.5 times of positive esters of silicon acis and the 3- aminopropyl triethoxysilanes of 0.06~0.07 times of ammonium hydroxide volume, in 20~30 DEG C with 200
~300 revs/min are stirred to react 12~15 hours；After reaction, by reaction solution with 2000~3000 revs/min centrifugation 10~
15 minutes, collect bottom precipitation；By the washes of absolute alcohol of 50~70 times of bottom precipitation weight of bottom precipitation, in 40~50
DEG C, it is 6~10 hours dry under conditions of 0.07~0.09MPa of vacuum degree, obtain Fe3O4@SiO2The mesoporous SiO of@2Magnetic Nano is micro-
Ball；
S4 weighs dopamine hydrochloride and the Tris buffer solutions of molar concentration 10mM, with solid-to-liquid ratio 1：(0.8~1.2) (mg/
ML it) mixes；Then add in Fe3O4@SiO2The mesoporous SiO of@2Magnetic Nano microsphere, Fe3O4@SiO2Magnetic Nano microsphere and dopamine
The mass ratio of hydrochloride is 1：(4~5) are stirred to react 16~20 hours in 20~30 DEG C with 200~300 revs/min；It has reacted
Reaction solution with 2000~3000 revs/min is centrifuged 10~15 minutes, collects bottom solid by Cheng Hou；By bottom solid bottom
After the deionized water washing of 100~200 times of absolute ethyl alcohol and bottom solid weight that 50~70 times of solid weight, in 50~60
DEG C, it is 6~10 hours dry under conditions of 0.07~0.09MPa of vacuum degree, obtain the Fe3O4@SiO2The mesoporous SiO of@2@PDA magnetic
Property nano material.
By in Fe3O4@SiO2The surface plating meso-porous titanium dioxide silicon layer of magnetic Nano microsphere nanoparticle, gained magnetism are received
Rice material material had not only had the stalling characteristic of magnetic material, but also the big specific surface area characteristic with mesoporous material, while mesoporous
The surface of silica carries out amino functional, improves the dispersion performance, magnetic property and absorption property of magnetic material.
The surfactant is one or more of polyethylene glycol, sodium citrate, ethylenediamine.
In some technical solutions of the present invention, preparing ferroso-ferric oxide makes four for not adding surfactant, obtaining
Although Fe 3 O pattern almost spherical, there are many incompleteness on surface, and spherical imperfect, this affects magnetic to a certain extent
The magnetic property and absorption property of property material.Four oxidations being prepared using polyvinyl alcohol and sodium citrate as surfactant
Three-iron, surface smoother, shape are spherical shape, and very completely, but particle diameter distribution is too wide.Especially using sodium citrate as surface
The ferroso-ferric oxide that activating agent is prepared, particle diameter distribution is very uneven, nanometer is differed from tens nanometers to hundreds of.And it uses
The ferroso-ferric oxide almost spherical that ethylenediamine is obtained as surfactant, surface is relatively rough, uniform in size, and particle diameter distribution is non-
It is often narrow.
The positive esters of silicon acis is tetraethyl orthosilicate and/or butyl silicate.Preferably, the positive esters of silicon acis is positive silicic acid
Tetra-ethyl ester and butyl silicate are with mass ratio 4：The mixture of 1 composition.
Relative to the prior art, the advantage of the invention is that：It is residual to the pesticide in agricultural product by Magnetic solid phases extraction
Carry out pre-treatment is stayed, processing time and cost can be substantially reduced, using the triple quadrupole rods tandem mass spectrometries of ultra performance liquid chromatography
Combined instrument is measured, and is measured more rapidly, qualitative more accurate.On the whole, the method for the present invention is quick, economical, efficiently and accurate,
Reduce the harmful effect to personnel and environment.
The accurate detecting method of Residual Pesticides in Farm Produce of the present invention has the operating time short, and organic reagent consumes
Less, the advantages that analysis cost is low, and analysis result is accurate.
Specific embodiment
By embodiment, the invention will be further described, but the present invention is not limited by following embodiment.
Agricultural product, the specific Xiaoqinling Nature Reserve for using Shanghai agricultural product central wholesale market (kind is Brassica rapa L).
Tetraethyl orthosilicate, No. CAS：562-90-3, purchased from Shanghai Ji Laide new materials Science and Technology Ltd..
Dopamine hydrochloride, No. CAS：62-31-7, purchased from AlfaAesar (China) Chemical Co., Ltd..
Tris (trishydroxymethylaminomethane) bufferings of the Tris buffer solutions of molar concentration 10mM, i.e. molar concentration 10mM
Liquid, purchased from Nantong Runzhou Chemical Co., Ltd..
Polyethylene glycol, No. CAS：25322-68-3, purchased from Shanghai Xi Long biochemical technologies Co., Ltd, molecular weight 8000.
Sodium citrate, No. CAS：6132-04-3, purchased from this hundred full chemistries (Shanghai) Co., Ltd..
Ethylenediamine, No. CAS：107-15-3, purchased from Shanghai Aladdin biochemical technology limited company.
Cetyl trimethylammonium bromide, No. CAS：57-09-0, purchased from AlfaAesar (China) Chemical Co., Ltd..
3- aminopropyl triethoxysilanes, No. CAS：919-30-2, purchased from Chemical Industry Co., Ltd. of earth of Hangzhou.
Butyl silicate, No. CAS：4766-57-8, purchased from Shanghai Mai Ruier chemical technologies Co., Ltd.
Instrument and the condition that use is analyzed in detection process are as follows：
Refiner is provided, model BILON by Shanghai than bright instrument manufacturing Co., Ltd.
Vortex oscillator, by water north science popularization laboratory apparatus factory of Jintan City, model XH-C.
The testing conditions of ultra performance liquid chromatography are as follows：U.S. Waters/ACQUITY/UPLC；Chromatographic column：The U.S.
Waters/Acquity/UPLC/BE hours/C18 chromatographic columns, specification are 1.7 μm, 2.1 × 100mm；Mobile phase A is acetonitrile, and B is
The volume fraction of formic acid is 0.1% aqueous solution；Flow velocity：0.4 milliliter per minute；Column temperature：35℃；Gradient：A is within 0~1 minute
5%~10%, remaining is B；A is 10%~20% within 1~2 minute, remaining is B；A is 20%~40% within 2~4 minutes, remaining is
B；A is 40%~90% within 4~7 minutes, remaining is B；7~9 minutes A are 90%~70%, and 9~12 minutes A are 70%~5%,
Remaining is B.
Mass Spectrometer Method condition is as follows：Mass spectrograph：Waters/Xevo TQ~S Micro；Electric spray ion source, it is positive and negative from
Son scans simultaneously, and multiple-reaction monitoring pattern, capillary voltage 3.20kV, 150 DEG C of ion source temperature, desolventizing gas is nitrogen, temperature
It is 500 DEG C to spend, 800L/ hours r of dry gas stream speed, and collision gas is argon gas, and argon gas flow velocity is 0.16mL/min；
The multiple-reaction monitoring condition is as follows：
Table 1 detects the title of pesticide and mass spectrum multiple-reaction monitoring qualitative, quantitative ion information
Embodiment 1
The accurate detecting method of Residual Pesticides in Farm Produce, is made of following step：
(1) 100g Xiaoqinling Nature Reserves refiner with 9500 revs/min is homogenized 1 minute, obtains slurries；5g slurries are taken in 50mL
In tool plug centrifuge tube, 20mL deionized waters and 2mL acetonitriles are then added in, is shaken 2 minutes with 1800 revs/min；
(2) 50mg magnetic Nano materials are added in into the tool plug centrifuge tube of step (1), are continued with 1800 revs/min of concussions 4
Minute；
(3) magnet is placed in centrifuge tube side wall, magnetic Nano material fully adsorbs the pesticide in agricultural product, has magnetism
Magnetic Nano material be attracted on the side wall by near magnet, discard the mixed liquor of agricultural product, acetonitrile and water, use 2mL every time
Deionized water cleans magnetic Nano material 3 times, discards cleaning solution；
(4) using organic solvent 4mL to tool fill in centrifuge tube in magnetic Nano material in ultrasonic power 300W, supersonic frequency
The condition ultrasound of 25kHz elutes 8 minutes, and the pesticide that magnetic nano-particle adsorbs is eluted in organic solvent, is then blown in nitrogen
Eluent is concentrated into 1mL on instrument, by 0.22 μm of the filter membrane in aperture, obtains prepare liquid；Wherein organic solvent is acetonitrile/methanol
With volume ratio 3：The mixed solvent of 1 composition；
(5) machine on is analyzed prepare liquid using the triple quadrupole rods tandem mass spectrometry combined instruments of ultra performance liquid chromatography, is adopted
Qualitative, quantitative measure is carried out with external standard working curve method, obtains the accurate measurement result of Residual Pesticides in Farm Produce.
The Fe3O4@SiO2The specific building-up process of@PDA magnetic Nano materials is：
S1 is by 1.35g FeCl3·6H2O and 75mL ethylene glycol mixes, and is stirred under magnetic stirring apparatus effect with 260 revs/min
It mixes 0.5 hour, then adds in 3.6g sodium acetates, continue to stir 1 hour with 260 revs/min, obtain mixed liquor；Mixed liquor is turned
It moves in the teflon lined stainless steel autoclave that capacity is 200mL, is reacted 12 hours in 200 DEG C of heating；It will be anti-
Product is answered to be separated and collected outside plus under magnetic fields, and with the washes of absolute alcohol of 60 times of reaction product weight, in 50 DEG C, vacuum
It spends 0.07MPa to be dried in vacuo 8 hours, obtains black solid Fe3O4Nanoparticle；
S2 is by 50mg Fe3O4Nanoparticle is added in the hydrochloric acid of 20mL molar concentrations 2mol/L, ultrasonic power 300W,
It is ultrasonically treated 5 minutes under conditions of supersonic frequency 25kHz, then uses Fe3O4The deionized water that 100 times of nanoparticle weight is by magnetic
Property Fe3O4Nanoparticle cleans up；Then by the Fe after cleaning3O4Nanoparticle adds in 200mL ethanol/waters volume ratio 4/1
Solution adds the concentrated ammonia liquor of 2.0mL mass fractions 28%, continues under conditions of ultrasonic power 300W, supersonic frequency 25kHz
It is ultrasonically treated 20 minutes, obtains mixed liquor；Then, by 1.0mL tetraethyl orthosilicates add in mixed liquor in, in 30 DEG C with 260 turns/
Minute is stirred to react 6 hours so that tetraethyl orthosilicate completes hydrolysis and polycondensation, collecting reaction product；By reaction product with instead
The washes of absolute alcohol of 50 times of products weight is answered, removes the silicon dioxide granule of blank, in 50 DEG C, vacuum degree 0.07MPa vacuum
It is 8 hours dry, obtain Fe3O4@SiO2Magnetic Nano microsphere；
S3 weighs 400mg dopamine hydrochlorides and the Tris buffer solutions mixing of 400mL molar concentrations 10mM；Then add in
100mgFe3O4@SiO2Magnetic Nano microsphere is stirred to react 16 hours in 25 DEG C with 300 revs/min；After the completion of reaction, it will react
Liquid is centrifuged 15 minutes with 2600 revs/min, collects bottom solid；By the absolute ethyl alcohol of 70 times of bottom solid weight of bottom solid
After being washed with 200 times of deionized water of bottom solid weight, it is dried in vacuo 10 hours in 50 DEG C, vacuum degree 0.07MPa, obtains institute
State Fe3O4@SiO2@PDA magnetic Nano materials.
Standard working solution is prepared：Appropriate each standard sample of pesticide is taken respectively, with acetontrile into 3~500 μ g/ in relative sample
The standard working solution of 7 concentration points in kg concentration ranges.
Using autosampler sample introduction, 5 μ L of sampling volume, using ultra performance liquid chromatography to agriculture to be measured in detection process
After medicine carries out quick separating, it is measured under electron spray (ESI) ionization source positive and negative ion multiple-reaction monitoring pattern.
Qualitative, quantitative measure is carried out using external standard working curve method, 15 kinds of pesticide residues are obtained by calculation in agricultural product
As a result.The standard working solution of each concentration gradient is carried out the triple quadrupole rods tandem mass spectrometries of ultra performance liquid chromatography to measure, with standard
The chromatographic peak area of the quota ion of each pesticide carries out regression analysis to its respective concentration in working solution, and it is bent to obtain standard work
Line；The prepare liquid in step (5) is measured under the same conditions, measures the quota ion chromatography of 15 kinds of pesticides in prepare liquid
Peak area, substitute into standard curve, obtain 15 kinds of pesticide concentrations in prepare liquid, then according to representated by prepare liquid sample quality meter
Calculation obtains the residual quantity of 15 kinds of pesticides in sample.
Every Testing index is shown in Table 2.
Table 2 detects the range of linearity, linear equation, related coefficient, detection limit and the recovery of standard addition of pesticide
Embodiment 2
Embodiment 2 is substantially the same manner as Example 1, differs only in：
The Fe3O4@SiO2The specific building-up process of@PDA magnetic Nano materials is：
S1 is by 1.35g FeCl3·6H2O and 75mL ethylene glycol mixes, and is stirred under magnetic stirring apparatus effect with 260 revs/min
It mixes 0.5 hour, then adds in 3.6g sodium acetates, continue to stir 1 hour with 260 revs/min；2.2g polyethylene glycol is continuously added,
It is stirred 15 minutes with 260 revs/min, obtains mixed liquor；By mixed liquor be transferred to capacity be 200mL teflon lined not
It becomes rusty in steel autoclave, is reacted 12 hours in 200 DEG C of heating；Reaction product is separated and collected outside plus under magnetic fields, and
With 60 times of washes of absolute alcohol of reaction product weight, it is dried in vacuo 8 hours in 50 DEG C, vacuum degree 0.07MPa, obtains black and consolidate
Body Fe3O4Nanoparticle；
S2 is by 50mg Fe3O4Nanoparticle is added in the hydrochloric acid of 20mL molar concentrations 2mol/L, ultrasonic power 300W,
It is ultrasonically treated 5 minutes under conditions of supersonic frequency 25kHz, then uses Fe3O4The deionized water that 100 times of nanoparticle weight is by magnetic
Property Fe3O4Nanoparticle cleans up；Then by the Fe after cleaning3O4Nanoparticle adds in 200mL ethanol/waters volume ratio 4/1
Solution adds the concentrated ammonia liquor of 2.0mL mass fractions 28%, continues under conditions of ultrasonic power 300W, supersonic frequency 25kHz
It is ultrasonically treated 20 minutes, obtains mixed liquor；Then, by 1.0mL tetraethyl orthosilicates add in mixed liquor in, in 30 DEG C with 260 turns/
Minute is stirred to react 6 hours so that tetraethyl orthosilicate completes hydrolysis and polycondensation, collecting reaction product；By reaction product with instead
The washes of absolute alcohol of 50 times of products weight is answered, removes the silicon dioxide granule of blank, in 50 DEG C, vacuum degree 0.07MPa vacuum
It is 8 hours dry, obtain Fe3O4@SiO2Magnetic Nano microsphere；
S3 weighs 400mg dopamine hydrochlorides and the Tris buffer solutions mixing of 400mL molar concentrations 10mM；Then add in
100mgFe3O4@SiO2Magnetic Nano microsphere is stirred to react 16 hours in 25 DEG C with 300 revs/min；After the completion of reaction, it will react
Liquid is centrifuged 15 minutes with 2600 revs/min, collects bottom solid；By the absolute ethyl alcohol of 70 times of bottom solid weight of bottom solid
After being washed with 200 times of deionized water of bottom solid weight, it is dried in vacuo 10 hours in 50 DEG C, vacuum degree 0.07MPa, obtains institute
State Fe3O4@SiO2@PDA magnetic Nano materials.
Table 3 detects the range of linearity, linear equation, related coefficient, detection limit and the recovery of standard addition of pesticide
Embodiment 3
Embodiment 3 is substantially the same manner as Example 1, differs only in：
The Fe3O4@SiO2The specific building-up process of@PDA magnetic Nano materials is：
S1 is by 1.35g FeCl3·6H2O and 75mL ethylene glycol mixes, and is stirred under magnetic stirring apparatus effect with 260 revs/min
It mixes 0.5 hour, then adds in 3.6g sodium acetates, continue to stir 1 hour with 260 revs/min；2.2g sodium citrates are continuously added,
It is stirred 15 minutes with 260 revs/min, obtains mixed liquor；By mixed liquor be transferred to capacity be 200mL teflon lined not
It becomes rusty in steel autoclave, is reacted 12 hours in 200 DEG C of heating；Reaction product is separated and collected outside plus under magnetic fields, and
With 60 times of washes of absolute alcohol of reaction product weight, it is dried in vacuo 8 hours in 50 DEG C, vacuum degree 0.07MPa, obtains black and consolidate
Body Fe3O4Nanoparticle；
S2 is by 50mg Fe3O4Nanoparticle is added in the hydrochloric acid of 20mL molar concentrations 2mol/L, ultrasonic power 300W,
It is ultrasonically treated 5 minutes under conditions of supersonic frequency 25kHz, then uses Fe3O4The deionized water that 100 times of nanoparticle weight is by magnetic
Property Fe3O4Nanoparticle cleans up；Then by the Fe after cleaning3O4Nanoparticle adds in 200mL ethanol/waters volume ratio 4/1
Solution adds the concentrated ammonia liquor of 2.0mL mass fractions 28%, continues under conditions of ultrasonic power 300W, supersonic frequency 25kHz
It is ultrasonically treated 20 minutes, obtains mixed liquor；Then, by 1.0mL tetraethyl orthosilicates add in mixed liquor in, in 30 DEG C with 260 turns/
Minute is stirred to react 6 hours so that tetraethyl orthosilicate completes hydrolysis and polycondensation, collecting reaction product；By reaction product with instead
The washes of absolute alcohol of 50 times of products weight is answered, removes the silicon dioxide granule of blank, in 50 DEG C, vacuum degree 0.07MPa vacuum
It is 8 hours dry, obtain Fe3O4@SiO2Magnetic Nano microsphere；
S3 weighs 400mg dopamine hydrochlorides and the Tris buffer solutions mixing of 400mL molar concentrations 10mM；Then add in
100mgFe3O4@SiO2Magnetic Nano microsphere is stirred to react 16 hours in 25 DEG C with 300 revs/min；After the completion of reaction, it will react
Liquid is centrifuged 15 minutes with 2600 revs/min, collects bottom solid；By the absolute ethyl alcohol of 70 times of bottom solid weight of bottom solid
After being washed with 200 times of deionized water of bottom solid weight, it is dried in vacuo 10 hours in 50 DEG C, vacuum degree 0.07MPa, obtains institute
State Fe3O4@SiO2@PDA magnetic Nano materials.
Table 4 detects the range of linearity, linear equation, related coefficient, detection limit and the recovery of standard addition of pesticide
Embodiment 4
Embodiment 4 is substantially the same manner as Example 1, differs only in：
The Fe3O4@SiO2The specific building-up process of@PDA magnetic Nano materials is：
S1 is by 1.35g FeCl3·6H2O and 75mL ethylene glycol mixes, and is stirred under magnetic stirring apparatus effect with 260 revs/min
It mixes 0.5 hour, then adds in 3.6g sodium acetates, continue to stir 1 hour with 260 revs/min；2.2g ethylenediamines are continuously added, with
260 revs/min are stirred 15 minutes, obtain mixed liquor；It is stainless that mixed liquor is transferred to the teflon lined that capacity is 200mL
In steel autoclave, reacted 12 hours in 200 DEG C of heating；Reaction product outside plus under magnetic fields is separated and collected, is used in combination
The washes of absolute alcohol that 60 times of reaction product weight is dried in vacuo 8 hours in 50 DEG C, vacuum degree 0.07MPa, obtains black solid
Fe3O4Nanoparticle；
S2 is by 50mg Fe3O4Nanoparticle is added in the hydrochloric acid of 20mL molar concentrations 2mol/L, ultrasonic power 300W,
It is ultrasonically treated 5 minutes under conditions of supersonic frequency 25kHz, then uses Fe3O4The deionized water that 100 times of nanoparticle weight is by magnetic
Property Fe3O4Nanoparticle cleans up；Then by the Fe after cleaning3O4Nanoparticle adds in 200mL ethanol/waters volume ratio 4/1
Solution adds the concentrated ammonia liquor of 2.0mL mass fractions 28%, continues under conditions of ultrasonic power 300W, supersonic frequency 25kHz
It is ultrasonically treated 20 minutes, obtains mixed liquor；Then, by 1.0mL tetraethyl orthosilicates add in mixed liquor in, in 30 DEG C with 260 turns/
Minute is stirred to react 6 hours so that tetraethyl orthosilicate completes hydrolysis and polycondensation, collecting reaction product；By reaction product with instead
The washes of absolute alcohol of 50 times of products weight is answered, removes the silicon dioxide granule of blank, in 50 DEG C, vacuum degree 0.07MPa vacuum
It is 8 hours dry, obtain Fe3O4@SiO2Magnetic Nano microsphere；
S3 weighs 400mg dopamine hydrochlorides and the Tris buffer solutions mixing of 400mL molar concentrations 10mM；Then add in
100mgFe3O4@SiO2Magnetic Nano microsphere is stirred to react 16 hours in 25 DEG C with 300 revs/min；After the completion of reaction, it will react
Liquid is centrifuged 15 minutes with 2600 revs/min, collects bottom solid；By the absolute ethyl alcohol of 70 times of bottom solid weight of bottom solid
After being washed with 200 times of deionized water of bottom solid weight, it is dried in vacuo 10 hours in 50 DEG C, vacuum degree 0.07MPa, obtains institute
State Fe3O4@SiO2@PDA magnetic Nano materials.
Table 5 detects the range of linearity, linear equation, related coefficient, detection limit and the recovery of standard addition of pesticide
Embodiment 5
Embodiment 5 is substantially the same manner as Example 1, differs only in：
The Fe3O4@SiO2The mesoporous SiO of@2The specific building-up process of@PDA magnetic Nano materials is：
S1 is by 1.35g FeCl3·6H2O and 75mL ethylene glycol mixes, and is stirred under magnetic stirring apparatus effect with 260 revs/min
It mixes 0.5 hour, then adds in 3.6g sodium acetates, continue to stir 1 hour with 260 revs/min；2.2g ethylenediamines are continuously added, with
260 revs/min are stirred 15 minutes, obtain mixed liquor；It is stainless that mixed liquor is transferred to the teflon lined that capacity is 200mL
In steel autoclave, reacted 12 hours in 200 DEG C of heating；Reaction product outside plus under magnetic fields is separated and collected, is used in combination
The washes of absolute alcohol that 60 times of reaction product weight is dried in vacuo 8 hours in 50 DEG C, vacuum degree 0.07MPa, obtains black solid
Fe3O4Nanoparticle；
S2 is by 50mg Fe3O4Nanoparticle is added in the hydrochloric acid of 20mL molar concentrations 2mol/L, ultrasonic power 300W,
It is ultrasonically treated 5 minutes under conditions of supersonic frequency 25kHz, then uses Fe3O4The deionized water that 100 times of nanoparticle weight is by magnetic
Property Fe3O4Nanoparticle cleans up；Then by the Fe after cleaning3O4Nanoparticle adds in 200mL ethanol/waters volume ratio 4/1
Solution adds the concentrated ammonia liquor of 2.0mL mass fractions 28%, continues under conditions of ultrasonic power 300W, supersonic frequency 25kHz
It is ultrasonically treated 20 minutes, obtains mixed liquor；Then, by 1.0mL tetraethyl orthosilicates add in mixed liquor in, in 30 DEG C with 260 turns/
Minute is stirred to react 6 hours so that tetraethyl orthosilicate completes hydrolysis and polycondensation, collecting reaction product；By reaction product with instead
The washes of absolute alcohol of 50 times of products weight is answered, removes the silicon dioxide granule of blank, in 50 DEG C, vacuum degree 0.07MPa vacuum
It is 8 hours dry, obtain Fe3O4@SiO2Magnetic Nano microsphere；
S3 is by Fe3O4@SiO2Magnetic Nano microsphere, absolute ethyl alcohol and deionized water are with 1：70：80 (g/mL/mL) are mixed,
It is ultrasonically treated 15 minutes under conditions of ultrasonic power 300W, supersonic frequency 25kHz；Then add in 0.17 times of deionized water volume
Mass fraction is 28% concentrated ammonia liquor and Fe3O4@SiO2The cetyl trimethylammonium bromide that 3 times of magnetic Nano microsphere weight, with
260 revs/min are stirred 30 minutes；Continuously add the tetraethyl orthosilicate of 0.5 times of ammonium hydroxide volume and the 3- of 0.07 times of ammonium hydroxide volume
Aminopropyl triethoxysilane is stirred to react 12 hours in 25 DEG C with 300 revs/min；After reaction, by reaction solution with 2000
Rev/min centrifugation 10 minutes, collect bottom precipitation；By the washes of absolute alcohol of 70 times of bottom precipitation weight of bottom precipitation, in
50 DEG C, it is 8 hours dry under conditions of vacuum degree 0.07MPa, obtain Fe3O4@SiO2The mesoporous SiO of@2Magnetic Nano microsphere；
S4 weighs 400mg dopamine hydrochlorides and the Tris buffer solutions mixing of 400mL molar concentrations 10mM；Then add in
100mg Fe3O4@SiO2The mesoporous SiO of@2Magnetic Nano microsphere is stirred to react 16 hours in 25 DEG C with 300 revs/min；It has reacted
Reaction solution with 2600 revs/min is centrifuged 15 minutes, collects bottom solid by Cheng Hou；By bottom solid bottom solid weight 70
After the washing of the deionized water of 200 times of absolute ethyl alcohol again and bottom solid weight, it is dried in vacuo in 50 DEG C, vacuum degree 0.07MPa
10 hours, obtain the Fe3O4@SiO2The mesoporous SiO of@2@PDA magnetic Nano materials.
Table 6 detects the range of linearity, linear equation, related coefficient, detection limit and the recovery of standard addition of pesticide
Embodiment 6
Embodiment 6 is substantially the same manner as Example 1, differs only in：
The Fe3O4@SiO2The specific building-up process of@PDA magnetic Nano materials is：
S1 is by 1.35g FeCl3·6H2O and 75mL ethylene glycol mixes, and is stirred under magnetic stirring apparatus effect with 260 revs/min
It mixes 0.5 hour, then adds in 3.6g sodium acetates, continue to stir 1 hour with 260 revs/min；2.2g ethylenediamines are continuously added, with
260 revs/min are stirred 15 minutes, obtain mixed liquor；It is stainless that mixed liquor is transferred to the teflon lined that capacity is 200mL
In steel autoclave, reacted 12 hours in 200 DEG C of heating；Reaction product outside plus under magnetic fields is separated and collected, is used in combination
The washes of absolute alcohol that 60 times of reaction product weight is dried in vacuo 8 hours in 50 DEG C, vacuum degree 0.07MPa, obtains black solid
Fe3O4Nanoparticle；
S2 is by 50mg Fe3O4Nanoparticle is added in the hydrochloric acid of 20mL molar concentrations 2mol/L, ultrasonic power 300W,
It is ultrasonically treated 5 minutes under conditions of supersonic frequency 25kHz, then uses Fe3O4The deionized water that 100 times of nanoparticle weight is by magnetic
Property Fe3O4Nanoparticle cleans up；Then by the Fe after cleaning3O4Nanoparticle adds in 200mL ethanol/waters volume ratio 4/1
Solution adds the concentrated ammonia liquor of 2.0mL mass fractions 28%, continues under conditions of ultrasonic power 300W, supersonic frequency 25kHz
It is ultrasonically treated 20 minutes, obtains mixed liquor；Then, 1.0mL butyl silicates are added in mixed liquor, in 30 DEG C with 260 revs/min
Clock is stirred to react 6 hours, collecting reaction product；By the washes of absolute alcohol of 50 times of reaction product weight of reaction product, remove
The silicon dioxide granule of blank is dried in vacuo 8 hours in 50 DEG C, vacuum degree 0.07MPa, obtains Fe3O4@SiO2Magnetic Nano is micro-
Ball；
S3 is by Fe3O4@SiO2Magnetic Nano microsphere, absolute ethyl alcohol and deionized water are with 1：70：80 (g/mL/mL) are mixed,
It is ultrasonically treated 15 minutes under conditions of ultrasonic power 300W, supersonic frequency 25kHz；Then add in 0.17 times of deionized water volume
Mass fraction is 28% concentrated ammonia liquor and Fe3O4@SiO2The cetyl trimethylammonium bromide that 3 times of magnetic Nano microsphere weight, with
260 revs/min are stirred 30 minutes；Continuously add the butyl silicate of 0.5 times of ammonium hydroxide volume and the 3- ammonia of 0.07 times of ammonium hydroxide volume
Propyl-triethoxysilicane is stirred to react 12 hours in 25 DEG C with 300 revs/min；After reaction, by reaction solution with 2000
Rev/min centrifugation 10 minutes, collect bottom precipitation；By the washes of absolute alcohol of 70 times of bottom precipitation weight of bottom precipitation, in
50 DEG C, it is 8 hours dry under conditions of vacuum degree 0.07MPa, obtain Fe3O4@SiO2The mesoporous SiO of@2Magnetic Nano microsphere；
S4 weighs 400mg dopamine hydrochlorides and the Tris buffer solutions mixing of 400mL molar concentrations 10mM；Then add in
100mg Fe3O4@SiO2The mesoporous SiO of@2Magnetic Nano microsphere is stirred to react 16 hours in 25 DEG C with 300 revs/min；It has reacted
Reaction solution with 2600 revs/min is centrifuged 15 minutes, collects bottom solid by Cheng Hou；By bottom solid bottom solid weight 70
After the washing of the deionized water of 200 times of absolute ethyl alcohol again and bottom solid weight, it is dried in vacuo in 50 DEG C, vacuum degree 0.07MPa
10 hours, obtain the Fe3O4@SiO2The mesoporous SiO of@2@PDA magnetic Nano materials.
Table 7 detects the range of linearity, linear equation, related coefficient, detection limit and the recovery of standard addition of pesticide
Embodiment 7
Embodiment 7 is substantially the same manner as Example 1, differs only in：
The Fe3O4@SiO2The specific building-up process of@PDA magnetic Nano materials is：
S1 is by 1.35g FeCl3·6H2O and 75mL ethylene glycol mixes, and is stirred under magnetic stirring apparatus effect with 260 revs/min
It mixes 0.5 hour, then adds in 3.6g sodium acetates, continue to stir 1 hour with 260 revs/min；2.2g ethylenediamines are continuously added, with
260 revs/min are stirred 15 minutes, obtain mixed liquor；It is stainless that mixed liquor is transferred to the teflon lined that capacity is 200mL
In steel autoclave, reacted 12 hours in 200 DEG C of heating；Reaction product outside plus under magnetic fields is separated and collected, is used in combination
The washes of absolute alcohol that 60 times of reaction product weight is dried in vacuo 8 hours in 50 DEG C, vacuum degree 0.07MPa, obtains black solid
Fe3O4Nanoparticle；
S2 is by 50mg Fe3O4Nanoparticle is added in the hydrochloric acid of 20mL molar concentrations 2mol/L, ultrasonic power 300W,
It is ultrasonically treated 5 minutes under conditions of supersonic frequency 25kHz, then uses Fe3O4The deionized water that 100 times of nanoparticle weight is by magnetic
Property Fe3O4Nanoparticle cleans up；Then by the Fe after cleaning3O4Nanoparticle adds in 200mL ethanol/waters volume ratio 4/1
Solution adds the concentrated ammonia liquor of 2.0mL mass fractions 28%, continues under conditions of ultrasonic power 300W, supersonic frequency 25kHz
It is ultrasonically treated 20 minutes, obtains mixed liquor；Then, the positive esters of silicon acis of 1.0mL is added in mixed liquor, in 30 DEG C with 260 revs/min
6 hours are stirred to react, collecting reaction product；By the washes of absolute alcohol of 50 times of reaction product weight of reaction product, sky is removed
White silicon dioxide granule is dried in vacuo 8 hours in 50 DEG C, vacuum degree 0.07MPa, obtains Fe3O4@SiO2Magnetic Nano microsphere；
Wherein described positive esters of silicon acis is tetraethyl orthosilicate and butyl silicate with mass ratio 4：The mixture of 1 composition；
S3 is by Fe3O4@SiO2Magnetic Nano microsphere, absolute ethyl alcohol and deionized water are with 1：70：80 (g/mL/mL) are mixed,
It is ultrasonically treated 15 minutes under conditions of ultrasonic power 300W, supersonic frequency 25kHz；Then add in 0.17 times of deionized water volume
Mass fraction is 28% concentrated ammonia liquor and Fe3O4@SiO2The cetyl trimethylammonium bromide that 3 times of magnetic Nano microsphere weight, with
260 revs/min are stirred 30 minutes；Continuously add the positive esters of silicon acis of 0.5 times of ammonium hydroxide volume and the 3- ammonia third of 0.07 times of ammonium hydroxide volume
Ethyl triethoxy silicane alkane is stirred to react 12 hours in 25 DEG C with 300 revs/min；After reaction, by reaction solution with 2000 turns/
Minute centrifugation 10 minutes, collects bottom precipitation；By the washes of absolute alcohol of 70 times of bottom precipitation weight of bottom precipitation, in 50
DEG C, it is 8 hours dry under conditions of vacuum degree 0.07MPa, obtain Fe3O4@SiO2The mesoporous SiO of@2Magnetic Nano microsphere；It is wherein described
Positive esters of silicon acis is tetraethyl orthosilicate and butyl silicate with mass ratio 4：The mixture of 1 composition；
S4 weighs 400mg dopamine hydrochlorides and the Tris buffer solutions mixing of 400mL molar concentrations 10mM；Then add in
100mg Fe3O4@SiO2The mesoporous SiO of@2Magnetic Nano microsphere is stirred to react 16 hours in 25 DEG C with 300 revs/min；It has reacted
Reaction solution with 2600 revs/min is centrifuged 15 minutes, collects bottom solid by Cheng Hou；By bottom solid bottom solid weight 70
After the washing of the deionized water of 200 times of absolute ethyl alcohol again and bottom solid weight, it is dried in vacuo in 50 DEG C, vacuum degree 0.07MPa
10 hours, obtain the Fe3O4@SiO2The mesoporous SiO of@2@PDA magnetic Nano materials.
Table 8 detects the range of linearity, linear equation, related coefficient, detection limit and the recovery of standard addition of pesticide
The above description is merely a specific embodiment, but protection scope of the present invention is not limited thereto, any
Those skilled in the art disclosed herein technical scope in, can without the variation that creative work is expected or
It replaces, should be covered by the protection scope of the present invention.Therefore, protection scope of the present invention should be limited with claims
Subject to fixed protection domain.
Claims (9)
1. the accurate detecting method of Residual Pesticides in Farm Produce, which is characterized in that be made of following step：
(1) agricultural product with refiner are homogenized, add in water and acetonitrile is disperseed；
(2) input magnetic Nano material carries out continuous concussion extraction；
(3) magnetic Nano material for extracting absorption pesticide is detached from agricultural product solution using magnet；
(4) magnetic Nano material for being adsorbed with pesticide is eluted using organic reagent, nitrogen blows concentration, and filtering obtains to be measured
Liquid；
(5) analysis detection is carried out to prepare liquid using ultra performance liquid chromatography triple quadrupole rods tandem mass spectrometry combined instruments.
2. the accurate detecting method of Residual Pesticides in Farm Produce according to claim 1, which is characterized in that by following step
Composition：
(1) 100~110g agricultural product with refiner are homogenized, obtain slurries；3~10g slurries is taken in 20~70mL to have to fill in
In centrifuge tube, 15~25mL deionized waters and 1~3mL acetonitriles are then added in, is shaken 2~5 minutes；
(2) 50~150mg magnetic Nano materials are added in into the tool plug centrifuge tube of step (1), continue concussion 3~10 minutes；
(3) magnet is placed in centrifuge tube side wall, magnetic Nano material fully adsorbs the pesticide in agricultural product, has magnetic magnetic
Property nano material is attracted on the side wall by near magnet, the mixed liquor of agricultural product, acetonitrile and water is discarded, with deionized water to magnetic
Property nano material clean 2~3 times, discard cleaning solution；
(4) magnetic Nano material ultrasound in centrifuge tube is filled in tool using 2~5mL of organic solvent to elute 5~10 minutes, magnetic Nano
The pesticide of particle absorption is eluted in organic solvent, obtains eluent；Then nitrogen blows concentrate eluant to 0.8~1.2mL, mistake
Filter, obtains prepare liquid；Wherein described organic solvent is acetonitrile and methanol with volume ratio (3~4)：The mixed solvent of 1 composition；
(5) machine on is analyzed prepare liquid using the triple quadrupole rods tandem mass spectrometry combined instruments of ultra performance liquid chromatography, using outer
It marks working curve method and carries out qualitative, quantitative measure, obtain the accurate measurement result of Residual Pesticides in Farm Produce.
3. the accurate detecting method of Residual Pesticides in Farm Produce according to claim 2, which is characterized in that in step (3)
The deionized water dosage of cleaning magnetic Nano material is 2~5mL every time.
4. the accurate detecting method of Residual Pesticides in Farm Produce according to claim 2, which is characterized in that in step (2)
The magnetic Nano material is Fe3O4@SiO2@PDA magnetic Nano materials or Fe3O4@SiO2The mesoporous SiO of@2@PDA magnetic Nanos
Material, wherein PDA are poly-dopamine.
5. the accurate detecting method of Residual Pesticides in Farm Produce according to claim 4, which is characterized in that the Fe3O4@
SiO2The specific building-up process of@PDA magnetic Nano materials is：
S1 is by FeCl3·6H2O is with ethylene glycol with solid-to-liquid ratio 1：(50~60) (g/mL) is mixed, with 200 under magnetic agitation effect
~300 revs/min are stirred 0.5~1 hour, then add in FeCl3·6H2The sodium acetate that 2.5~3 times of O weight, continue with 200~
300 revs/min are stirred 0.5~1 hour, obtain mixed liquor；It is anti-that mixed liquor is transferred to teflon lined stainless steel high pressure
It answers in kettle, is reacted 10~13 hours in 180~200 DEG C of heating；Reaction product outside plus under magnetic fields is separated and collected, is used in combination
The washes of absolute alcohol that 40~60 times of reaction product weight, it is dry under conditions of 40~50 DEG C, 0.07~0.09MPa of vacuum degree
6~10 hours, obtain black solid Fe3O4Nanoparticle；
S2 is by Fe3O4Nanoparticle is with solid-to-liquid ratio (2~3)：1 (mg/mL) is added in the hydrochloric acid of 1~2mol/L of molar concentration,
It is ultrasonically treated 5~10 minutes under conditions of 200~500W of ultrasonic power, 25~35kHz of supersonic frequency, then uses Fe3O4Nanometer is micro-
The deionized water that 80~200 times of ball weight is by Fe3O4Nanoparticle cleans up；Then by the Fe after cleaning3O4Nanoparticle adds
Enter the mixed solution of the ethanol/water volume ratio 4/1 of 8~12 times of hydrochloric acid volume, add the quality of 0.09~0.1 times of hydrochloric acid volume
The concentrated ammonia liquor of score 28% continues to be ultrasonically treated 10 under conditions of 200~500W of ultrasonic power, 25~35kHz of supersonic frequency
~30 minutes, obtain mixed liquor；Then, the positive esters of silicon acis of 0.04~0.05 times of hydrochloric acid volume is added in mixed liquor, in 25~
30 DEG C are stirred to react 5~7 hours with 200~300 revs/min so that positive esters of silicon acis completes hydrolysis and polycondensation, collects reaction production
Object；With 50~70 times of washes of absolute alcohol of reaction product weight, in 50~60 DEG C, the condition of 0.07~0.09MPa of vacuum degree
Lower drying 6~10 hours, obtains Fe3O4@SiO2Magnetic Nano microsphere；
S3 weighs dopamine hydrochloride and the Tris buffer solutions of molar concentration 10mM, with solid-to-liquid ratio 1：(0.8~1.2) (mg/mL)
Mixing；Then add in Fe3O4@SiO2Magnetic Nano microsphere, Fe3O4@SiO2The quality of magnetic Nano microsphere and dopamine hydrochloride
Than being 1：(4~5) are stirred to react 16~20 hours in 20~30 DEG C with 200~300 revs/min；After the completion of reaction, it will react
Liquid is centrifuged 10~15 minutes with 2000~3000 revs/min, collects bottom solid；By bottom solid with bottom solid weight 50~
After the deionized water washing of 70 times of 100~200 times of absolute ethyl alcohol and bottom solid weight, in 50~60 DEG C, vacuum degree 0.07
It is 6~10 hours dry under conditions of~0.09MPa, obtain the Fe3O4@SiO2@PDA magnetic Nano materials.
6. the accurate detecting method of Residual Pesticides in Farm Produce according to claim 4, which is characterized in that the Fe3O4@
SiO2The specific building-up process of@PDA magnetic Nano materials is：
S1 is by FeCl3·6H2O is with ethylene glycol with solid-to-liquid ratio 1：(50~60) (g/mL) is mixed, with 200 under magnetic agitation effect
~300 revs/min are stirred 0.5~1 hour, then add in FeCl3·6H2The sodium acetate that 2.5~3 times of O weight, continue with 200~
300 revs/min are stirred 0.5~1 hour；Continuously add FeCl3·6H2The surfactant that 1.6~2 times of O weight, with 200~
300 revs/min are stirred 15~25 minutes, obtain mixed liquor；It is anti-that mixed liquor is transferred to teflon lined stainless steel high pressure
It answers in kettle, is reacted 10~13 hours in 180~200 DEG C of heating；Reaction product outside plus under magnetic fields is separated and collected, is used in combination
The washes of absolute alcohol that 40~60 times of reaction product weight, it is dry under conditions of 40~50 DEG C, 0.07~0.09MPa of vacuum degree
6~10 hours, obtain black solid Fe3O4Nanoparticle；
S2 is by Fe3O4Nanoparticle is with solid-to-liquid ratio (2~3)：1 (mg/mL) is added in the hydrochloric acid of 1~2mol/L of molar concentration,
It is ultrasonically treated 5~10 minutes under conditions of 200~500W of ultrasonic power, 25~35kHz of supersonic frequency, then uses Fe3O4Nanometer is micro-
The deionized water that 80~200 times of ball weight is by Fe3O4Nanoparticle cleans up；Then by the Fe after cleaning3O4Nanoparticle adds
Enter the mixed solution of the ethanol/water volume ratio 4/1 of 8~12 times of hydrochloric acid volume, add the quality of 0.09~0.1 times of hydrochloric acid volume
The concentrated ammonia liquor of score 28% continues to be ultrasonically treated 10 under conditions of 200~500W of ultrasonic power, 25~35kHz of supersonic frequency
~30 minutes, obtain mixed liquor；Then, the positive esters of silicon acis of 0.04~0.05 times of hydrochloric acid volume is added in mixed liquor, in 25~
30 DEG C are stirred to react 5~7 hours with 200~300 revs/min so that positive esters of silicon acis completes hydrolysis and polycondensation, collects reaction production
Object；With 50~70 times of washes of absolute alcohol of reaction product weight, in 50~60 DEG C, the condition of 0.07~0.09MPa of vacuum degree
Lower drying 6~10 hours, obtains Fe3O4@SiO2Magnetic Nano microsphere；
S3 weighs dopamine hydrochloride and the Tris buffer solutions of molar concentration 10mM, with solid-to-liquid ratio 1：(0.8~1.2) (mg/mL)
Mixing；Then add in Fe3O4@SiO2Magnetic Nano microsphere, Fe3O4@SiO2The quality of magnetic Nano microsphere and dopamine hydrochloride
Than being 1：(4~5) are stirred to react 16~20 hours in 20~30 DEG C with 200~300 revs/min；After the completion of reaction, it will react
Liquid is centrifuged 10~15 minutes with 2000~3000 revs/min, collects bottom solid；By bottom solid with bottom solid weight 50~
After the deionized water washing of 70 times of 100~200 times of absolute ethyl alcohol and bottom solid weight, in 50~60 DEG C, vacuum degree 0.07
It is 6~10 hours dry under conditions of~0.09MPa, obtain the Fe3O4@SiO2@PDA magnetic Nano materials.
7. the accurate detecting method of Residual Pesticides in Farm Produce according to claim 4, which is characterized in that the Fe3O4@
SiO2The mesoporous SiO of@2The specific building-up process of@PDA magnetic Nano materials is：
S1 is by FeCl3·6H2O is with ethylene glycol with solid-to-liquid ratio 1：(50~60) (g/mL) is mixed, with 200 under magnetic agitation effect
~300 revs/min are stirred 0.5~1 hour, then add in FeCl3·6H2The sodium acetate that 2.5~3 times of O weight, continue with 200~
300 revs/min are stirred 0.5~1 hour；Continuously add FeCl3·6H2The surfactant that 1.6~2 times of O weight, with 200~
300 revs/min are stirred 15~25 minutes, obtain mixed liquor；It is anti-that mixed liquor is transferred to teflon lined stainless steel high pressure
It answers in kettle, is reacted 10~13 hours in 180~200 DEG C of heating；Reaction product outside plus under magnetic fields is separated and collected, is used in combination
The washes of absolute alcohol that 40~60 times of reaction product weight, it is dry under conditions of 40~50 DEG C, 0.07~0.09MPa of vacuum degree
6~10 hours, obtain black solid Fe3O4Nanoparticle；
S2 is by Fe3O4Nanoparticle is with solid-to-liquid ratio (2~3)：1 (mg/mL) is added in the hydrochloric acid of 1~2mol/L of molar concentration,
It is ultrasonically treated 5~10 minutes under conditions of 200~500W of ultrasonic power, 25~35kHz of supersonic frequency, then uses Fe3O4Nanometer is micro-
The deionized water that 80~200 times of ball weight is by Fe3O4Nanoparticle cleans up；Then by the Fe after cleaning3O4Nanoparticle adds
Enter the mixed solution of the ethanol/water volume ratio 4/1 of 8~12 times of hydrochloric acid volume, add the quality of 0.09~0.1 times of hydrochloric acid volume
The concentrated ammonia liquor of score 28% continues to be ultrasonically treated 10 under conditions of 200~500W of ultrasonic power, 25~35kHz of supersonic frequency
~30 minutes, obtain mixed liquor；Then, the positive esters of silicon acis of 0.04~0.05 times of hydrochloric acid volume is added in mixed liquor, in 25~
30 DEG C are stirred to react 5~7 hours with 200~300 revs/min so that positive esters of silicon acis completes hydrolysis and polycondensation, collects reaction production
Object；With 50~70 times of washes of absolute alcohol of reaction product weight, in 50~60 DEG C, the condition of 0.07~0.09MPa of vacuum degree
Lower drying 6~10 hours, obtains Fe3O4@SiO2Magnetic Nano microsphere；
S3 is by Fe3O4@SiO2Magnetic Nano microsphere, absolute ethyl alcohol and deionized water are with 1：(60~80)：80 (g/mL/mL) are mixed,
It is ultrasonically treated 15~20 minutes under conditions of 200~500W of ultrasonic power, 25~35kHz of supersonic frequency；Then add in go from
The mass fraction of sub- 0.17~0.2 times of water volume is 28% concentrated ammonia liquor and Fe3O4@SiO22~3 times of magnetic Nano microsphere weight
Cetyl trimethylammonium bromide, with 200~300 revs/min stir 30~40 minutes；Continuously add ammonium hydroxide volume 0.4~
0.5 times of positive esters of silicon acis and the 3- aminopropyl triethoxysilanes of 0.06~0.07 times of ammonium hydroxide volume, in 20~30 DEG C with 200~
300 revs/min are stirred to react 12~15 hours；After reaction, by reaction solution with 2000~3000 revs/min of centrifugations 10~15
Minute, collect bottom precipitation；By the washes of absolute alcohol of 50~70 times of bottom precipitation weight of bottom precipitation, in 40~50 DEG C,
It is 6~10 hours dry under conditions of 0.07~0.09MPa of vacuum degree, obtain Fe3O4@SiO2The mesoporous SiO of@2Magnetic Nano microsphere；
S4 weighs dopamine hydrochloride and the Tris buffer solutions of molar concentration 10mM, with solid-to-liquid ratio 1：(0.8~1.2) (mg/mL)
Mixing；Then add in Fe3O4@SiO2The mesoporous SiO of@2Magnetic Nano microsphere, Fe3O4@SiO2Magnetic Nano microsphere and dopamine hydrochloric acid
The mass ratio of salt is 1：(4~5) are stirred to react 16~20 hours in 20~30 DEG C with 200~300 revs/min；Reaction is completed
Afterwards, reaction solution with 2000~3000 revs/min is centrifuged 10~15 minutes, collects bottom solid；Bottom solid bottom is consolidated
After the washing of the deionized water of 100~200 times of the absolute ethyl alcohol that 50~70 times of body weight and bottom solid weight, in 50~60 DEG C,
It is 6~10 hours dry under conditions of 0.07~0.09MPa of vacuum degree, obtain the Fe3O4@SiO2The mesoporous SiO of@2@PDA magnetism is received
Rice material.
8. the accurate detecting method of the Residual Pesticides in Farm Produce described according to claim 6 or 7, which is characterized in that the table
Face activating agent is one or more of polyethylene glycol, sodium citrate, ethylenediamine.
9. the accurate detecting method of the Residual Pesticides in Farm Produce according to any one of claim 5-7, which is characterized in that
The positive esters of silicon acis is tetraethyl orthosilicate and/or butyl silicate.
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