CN108918736A - Using Magnetic solid phases abstraction technique to the detection method of fruit, vegetable pesticide residue - Google Patents
Using Magnetic solid phases abstraction technique to the detection method of fruit, vegetable pesticide residue Download PDFInfo
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
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Abstract
The invention discloses a kind of using Magnetic solid phases abstraction technique to the detection method of fruit, vegetable pesticide residue, includes the following steps:(1) it is homogenized;(2) concussion extraction;(3) adsorbing separation;(4) it elutes, nitrogen blows concentration, filters;(5) analysis detection.The present invention carries out pre-treatment using Magnetic solid phases abstraction technique, and once-through operation is completed to extract and purify two steps, and easy to operate, save trouble and labor, low in cost.The present invention is using nonpolar chromatographic column as one-dimensional column, polarity chromatographic column is as two-dimensional columns, a variety of determinands are first separated by molecular size when passing through one-dimensional non-polar column, using being separated again by polarity again when two-dimentional polarity chromatographic column, therefore it can reach the separating effect of GC × GC, complex matrices are enable to be efficiently separated, therefore the method for the present invention can carry out single injected sampling to Multiple Pesticides residual in complex matrices and analyze simultaneously.
Description
Technical field
The invention belongs to analyze testing field, it is related to a kind of more to fruit, pesticide in vegetable using Magnetic solid phases abstraction technique
Remaining detection method, and in particular to a kind of to combine solid state heat modulation comprehensive two dimensional gas chromatography mass spectrum to join using Magnetic solid phases extraction
With the how remaining method of pesticide in technology analysis fruit and vegetable.
Background technique
Pesticide Residue is paid close attention to by people always in agricultural product and environmental area, currently, the pesticide of domestic by-products
Residue detection is typically all reference《The measurement GB/T5009.218-2008 of persticide residue in fruits and vegetables》Or《Agricultural production
500 kinds of pesticides and the measurement gas chromatography-mass spectrography GB of related chemicals residual quantity in the safe national standard fruits and vegetables of product
23200.8-2016》And《The measurement gas chromatography-mass spectrography NY/T 1380 of 51 kinds of pesticide multi-residues in veterinary antibiotics~
2007》, the pretreatment process general steps of these reference standards are more, and there are two obvious disadvantages:One the disadvantage is that extract
Process needs to use the very high organic reagent of a large amount of purity, and these reagents are not only expensive, and can be to experimenter's body
Body health causes different degrees of harm;Another disadvantage is that purification process need it is small using expensive various solid phase adsorptions
Column, these reagents and pillar must obtain appropriate processing again after use, generally time-consuming, laborious, and cost is high.Such as
Fruit can be realized quick, simple, effective and cheap pre-treatment combination single injected sampling quickly and accurately screening confirmation agricultural production
Farm chemical ingredients in product, this is the target of various countries researcher many years.Still further aspect, with the increasingly increase of pesticide variety, with
And the difference of different agricultural product matrix, existing common pesticide residue analysis method, including gas chromatography, liquid chromatography,
There is different degrees of component and flow out phenomenon altogether in combined gas chromatography mass spectrometry, liquid chromatography mass combination method etc., i.e., to be measured
It cannot be efficiently separated between pesticide composition, between pesticide to be measured and matrix components, interfere the accuracy and reliability of result.For
The separation of complex sample, comprehensive two dimensional gas chromatography have a clear superiority.It uses two chromatographic columns of different nature, from first
Sample introduction is to the second root chromatogram column again after modulator carries out enrichment method for all components of chromatographic column outflow, due to two chromatographies
Post separation polarity is different, can be separated in the second root chromatogram column in the compound that the first root chromatogram column is not separated by, and realizes
The effect of so-called " orthogonal separation ", greatly improves peak capacity, reduces interference, while can also significantly improve sensitivity.
Comprehensive two dimensional gas chromatography and mass spectrometric hyphenated technique can largely meet Common Fruits and Determination of Multiple Pesticide Residues in Vegetables
The quickly demand of analysis and accurate qualitative, quantitative.
There are some research and utilization comprehensive two-dimensional gas chromatographies to analyze pesticide residue at present, but has generally all adopted
With jet-propelled refrigerant modulation technique.This technology needs a large amount of refrigerant gas generated using liquid nitrogen or refrigeration machine to be adjusted
System, general consumption is big, inconvenient to use.Under normal frequency of use, common liquid nitrogen container (250L) can only be maintained 1 week or so
Time.Very big challenge also proposed to the guarantee of the refrigerants such as liquid nitrogen in this way.In addition, this jet-propelled refrigerant modulation technique
A period of time preparation is required when opening and closing equipment, affects working efficiency.So it is limited to conditions present, this skill
Art is difficult to be promoted and applied in common lab at present.The solid state heat modulation technique invented in recent years uses semiconductor refrigerating,
The use of refrigerant has thoroughly been abandoned, it is easy to operate, substantially without maintenance, daily maintenance time and expense is greatly saved, and
And can run without interruption for a long time, it is obviously improved working efficiency, is suitble to use in conventional analysis laboratory.
Summary of the invention
In view of the problems of the existing technology, it is an object of the invention to design provide it is a kind of simple, quickly, it is accurate, can
The whole process analysis method for Common Fruits Determination of Multiple Pesticide Residues in Vegetables leaned on, be easy to promote the use of in common lab.
In order to solve the above technical problems, technical solution proposed by the present invention is:Using magnetic Nano material to agricultural product sample
Product carry out pre-treatment, how residual to Common Fruits pesticide residues in vegetables medicine using solid state heat modulation comprehensive two dimensional gas chromatography mass spectrometric hyphenated technique
The method for staying the carry out analysis detection of component.
It is a kind of using Magnetic solid phases abstraction technique to the detection method of fruit, vegetable pesticide residue, include the following steps:
(1) agricultural product are homogenized with refiner, water is added and acetonitrile is dispersed;
(2) investment magnetic Nano material carries out continuous concussion extraction;
(3) magnetic Nano material of extraction absorption pesticide is separated 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 solid state heat modulation comprehensive two dimensional gas chromatography mass spectrometer.
Specifically, it is of the present invention using Magnetic solid phases abstraction technique to the detection method of fruit, vegetable pesticide residue, by
Following step composition:
(1) 100~150g agricultural product are homogenized with refiner, obtain slurries;Take 5~15g slurries in 20~80mL
In tool plug centrifuge tube, 15~40mL water and 1~3mL acetonitrile is then added, shakes 2~6 minutes;
(2) 50~150mg magnetic Nano material is added into the tool plug centrifuge tube of step (1), continues concussion 3~9 minutes;
(3) magnet is placed in centrifuge tube side wall, magnetic Nano material sufficiently adsorbs the pesticide in agricultural product, has magnetism
Magnetic Nano material be attracted on the side wall of near magnet, the mixed liquor of agricultural product, acetonitrile and water is discarded, with water to magnetism
Nano material is cleaned 2~3 times, and cleaning solution is discarded;
(4) magnetic Nano material ultrasound in tool plug centrifuge tube is eluted 3~9 minutes using 2~5mL of organic solvent, it is magnetic
The pesticide of nanoparticle absorption is eluted in organic solvent, obtains eluent;Then eluent is concentrated into using nitrogen evaporator
0.8~1.2mL, filtering, obtains prepare liquid;
(5) machine analyzes prepare liquid using solid state heat modulation comprehensive two dimensional gas chromatography mass spectrometer on, before sample introduction
Internal standard working solution is added, qualitative, quantitative measurement is carried out using internal mark working curve method, obtains point of more pesticide residues in agricultural product
Analyse result.
Preferably, organic solvent described in step (4) is acetonitrile and methanol with volume ratio (3~4):The mixing of 1 composition is molten
Agent.
Preferably, cleaning the water consumption of magnetic Nano material in step (3) every time is 2~5mL.
Preferably, magnetic Nano material described in step (2) is Fe3O4@SiO2@PDA
Preferably, magnetic Nano material described in step (2) is Fe3O4@SiO2The mesoporous SiO of@2@PDA。
Wherein PDA is poly-dopamine.
The Fe3O4@SiO2The specific synthesis process of@PDA is:
S1 is by FeCl3·6H2O and ethylene glycol are with solid-to-liquid ratio 1:(50~60) (g/mL) mixing, magnetic agitation effect under with
200~300 revs/min are stirred 0.5~1 hour, and FeCl is then added3·6H2The sodium acetate that 2.5~3 times of O weight, continue with
200~300 revs/min are stirred 0.5~1 hour, and mixed liquor is obtained;It is high that mixed liquor is transferred to teflon lined stainless steel
It presses in reaction kettle, is reacted 10~13 hours in 180~200 DEG C of heating;Reaction product is separated and collected under the action of an external magnetic field,
And with 40~60 times of reaction product weight of washes of absolute alcohol, under conditions of 40~50 DEG C, 0.07~0.09MPa of vacuum degree
It is 6~10 hours dry, obtain black solid Fe3O4Nanosphere;
S2 is by Fe3O4Nanosphere 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 water that 80~200 times of nanosphere weight is by Fe3O4Nanosphere cleans up;Then by the Fe after cleaning3O4Nanosphere adds
The mixed solution for entering 8~12 times of hydrochloric acid volume of ethanol/water volume ratio 4/1 adds 0.09~0.1 times of hydrochloric acid volume of quality
The concentrated ammonia liquor of score 28%, continuation are ultrasonically treated 10 under conditions of 200~500W of ultrasonic power, 25~35kHz of supersonic frequency
~30 minutes, obtain mixed liquor;Then, 0.04~0.05 times of hydrochloric acid volume of positive esters of silicon acis is added in mixed liquor, in 25~
30 DEG C are stirred to react 5~7 hours with 200~300 revs/min, collecting reaction product;With 50~70 times of nothing of reaction product weight
Water-ethanol cleaning, it is 6~10 hours dry under conditions of 50~60 DEG C, 0.07~0.09MPa of vacuum degree, obtain Fe3O4@SiO2;
S3 weighs dopamine hydrochloride and the Tris buffer of molar concentration 10mM, with solid-to-liquid ratio 1:(0.8~1.2) (mg/
ML it) mixes;Fe is then added3O4@SiO2, Fe3O4@SiO2Mass ratio with dopamine hydrochloride is 1:(4~5), in 20~30
It DEG C is stirred to react 16~20 hours with 200~300 revs/min;After the reaction was completed, by reaction solution with 2000~3000 revs/min
Bottom solid is collected in centrifugation 10~15 minutes;Dehydrated alcohol and bottom by bottom solid with 50~70 times of bottom solid weight
After the water washing that 100~200 times of solid weight, dry 6~10 under conditions of 50~60 DEG C, 0.07~0.09MPa of vacuum degree
Hour, obtain the Fe3O4@SiO2@PDA。
As the improved technical solution of the present invention, the Fe3O4@SiO2The specific synthesis process of@PDA is:
S1 is by FeCl3·6H2O and ethylene glycol are with solid-to-liquid ratio 1:(50~60) (g/mL) mixing, magnetic agitation effect under with
200~300 revs/min are stirred 0.5~1 hour, and FeCl is then added3·6H2The 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, and mixed liquor is obtained;It is high that mixed liquor is transferred to teflon lined stainless steel
It presses in reaction kettle, is reacted 10~13 hours in 180~200 DEG C of heating;Reaction product is separated and collected under the action of an external magnetic field,
And with 40~60 times of reaction product weight of washes of absolute alcohol, under conditions of 40~50 DEG C, 0.07~0.09MPa of vacuum degree
It is 6~10 hours dry, obtain black solid Fe3O4Nanosphere;
S2 is by Fe3O4Nanosphere 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 water that 80~200 times of nanosphere weight is by Fe3O4Nanosphere cleans up;Then by the Fe after cleaning3O4Nanosphere adds
The mixed solution for entering 8~12 times of hydrochloric acid volume of ethanol/water volume ratio 4/1 adds 0.09~0.1 times of hydrochloric acid volume of quality
The concentrated ammonia liquor of score 28%, continuation are ultrasonically treated 10 under conditions of 200~500W of ultrasonic power, 25~35kHz of supersonic frequency
~30 minutes, obtain mixed liquor;Then, 0.04~0.05 times of hydrochloric acid volume of positive esters of silicon acis is added in mixed liquor, in 25~
30 DEG C are stirred to react 5~7 hours with 200~300 revs/min, collecting reaction product;With 50~70 times of nothing of reaction product weight
Water-ethanol cleaning, it is 6~10 hours dry under conditions of 50~60 DEG C, 0.07~0.09MPa of vacuum degree, obtain Fe3O4@SiO2;
S3 weighs dopamine hydrochloride and the Tris buffer of molar concentration 10mM, with solid-to-liquid ratio 1:(0.8~1.2) (mg/
ML it) mixes;Fe is then added3O4@SiO2, Fe3O4@SiO2Mass ratio with dopamine hydrochloride is 1:(4~5), in 20~30
It DEG C is stirred to react 16~20 hours with 200~300 revs/min;After the reaction was completed, by reaction solution with 2000~3000 revs/min
Bottom solid is collected in centrifugation 10~15 minutes;Dehydrated alcohol and bottom by bottom solid with 50~70 times of bottom solid weight
After the water washing that 100~200 times of solid weight, dry 6~10 under conditions of 50~60 DEG C, 0.07~0.09MPa of vacuum degree
Hour, obtain the Fe3O4@SiO2@PDA。
It is further preferred that the Fe3O4@SiO2The mesoporous SiO of@2The specific synthesis process of@PDA is:
S1 is by FeCl3·6H2O and ethylene glycol are with solid-to-liquid ratio 1:(50~60) (g/mL) mixing, magnetic agitation effect under with
200~300 revs/min are stirred 0.5~1 hour, and FeCl is then added3·6H2The 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, and mixed liquor is obtained;It is high that mixed liquor is transferred to teflon lined stainless steel
It presses in reaction kettle, is reacted 10~13 hours in 180~200 DEG C of heating;Reaction product is separated and collected under the action of an external magnetic field,
And with 40~60 times of reaction product weight of washes of absolute alcohol, under conditions of 40~50 DEG C, 0.07~0.09MPa of vacuum degree
It is 6~10 hours dry, obtain black solid Fe3O4Nanosphere;
S2 is by Fe3O4Nanosphere 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 water that 80~200 times of nanosphere weight is by Fe3O4Nanosphere cleans up;Then by the Fe after cleaning3O4Nanosphere adds
The mixed solution for entering 8~12 times of hydrochloric acid volume of ethanol/water volume ratio 4/1 adds 0.09~0.1 times of hydrochloric acid volume of quality
The concentrated ammonia liquor of score 28%, continuation are ultrasonically treated 10 under conditions of 200~500W of ultrasonic power, 25~35kHz of supersonic frequency
~30 minutes, obtain mixed liquor;Then, 0.04~0.05 times of hydrochloric acid volume of positive esters of silicon acis is added in mixed liquor, in 25~
30 DEG C are stirred to react 5~7 hours with 200~300 revs/min, collecting reaction product;With 50~70 times of nothing of reaction product weight
Water-ethanol cleaning, it is 6~10 hours dry under conditions of 50~60 DEG C, 0.07~0.09MPa of vacuum degree, obtain Fe3O4@SiO2;
S3 is by Fe3O4@SiO2, dehydrated alcohol and water is with 1:(60~80):80 (g/mL/mL) mixing, in ultrasonic power 200
It is ultrasonically treated 15~20 minutes under conditions of~500W, 25~35kHz of supersonic frequency;Then it is added 0.17~0.2 times of water volume
Mass fraction be 28% concentrated ammonia liquor and Fe3O4@SiO2The cetyl trimethylammonium bromide that 2~3 times of weight, with 200~
300 revs/min are stirred 30~40 minutes;Continuously add 0.4~0.5 times of ammonium hydroxide volume positive esters of silicon acis and ammonium hydroxide volume 0.06~
0.07 times of 3- aminopropyl triethoxysilane is stirred to react 12~15 hours in 20~30 DEG C with 200~300 revs/min;Instead
After answering, reaction solution is centrifuged 10~15 minutes with 2000~3000 revs/min, collects bottom precipitation;Bottom precipitation is used
The washes of absolute alcohol that 50~70 times of bottom precipitation weight, it is dry under conditions of 40~50 DEG C, 0.07~0.09MPa of vacuum degree
6~10 hours, obtain Fe3O4@SiO2The mesoporous SiO of@2;
S4 weighs dopamine hydrochloride and the Tris buffer of molar concentration 10mM, with solid-to-liquid ratio 1:(0.8~1.2) (mg/
ML it) mixes;Fe is then added3O4@SiO2The mesoporous SiO of@2, Fe3O4@SiO2The mesoporous SiO of@2Mass ratio with dopamine hydrochloride is
1:(4~5) are stirred to react 16~20 hours in 20~30 DEG C with 200~300 revs/min;After the reaction was completed, by reaction solution with
2000~3000 revs/min are centrifuged 10~15 minutes, collect bottom solid;By bottom solid with 50~70 times of bottom solid weight
Dehydrated alcohol and 100~200 times of bottom solid weight of water washing after, in 50~60 DEG C, 0.07~0.09MPa of vacuum degree
Under the conditions of dry 6~10 hours, obtain the Fe3O4@SiO2The mesoporous SiO of@2@PDA。
It is further preferred that the Fe3O4@SiO2The mesoporous SiO of@2The specific synthesis process of@PDA is:
S1 is by FeCl3·6H2O and ethylene glycol are with solid-to-liquid ratio 1:(50~60) (g/mL) mixing, magnetic agitation effect under with
200~300 revs/min are stirred 0.5~1 hour, and FeCl is then added3·6H2The 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, and mixed liquor is obtained;It is high that mixed liquor is transferred to teflon lined stainless steel
It presses in reaction kettle, is reacted 10~13 hours in 180~200 DEG C of heating;Reaction product is separated and collected under the action of an external magnetic field,
And with 40~60 times of reaction product weight of washes of absolute alcohol, under conditions of 40~50 DEG C, 0.07~0.09MPa of vacuum degree
It is 6~10 hours dry, obtain black solid Fe3O4Nanosphere;
S2 is by Fe3O4Nanosphere 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 water that 80~200 times of nanosphere weight is by Fe3O4Nanosphere cleans up;Then by the Fe after cleaning3O4Nanosphere adds
The mixed solution for entering 8~12 times of hydrochloric acid volume of ethanol/water volume ratio 4/1 adds 0.09~0.1 times of hydrochloric acid volume of quality
The concentrated ammonia liquor of score 28%, continuation are ultrasonically treated 10 under conditions of 200~500W of ultrasonic power, 25~35kHz of supersonic frequency
~30 minutes, obtain mixed liquor;Then, 0.04~0.05 times of hydrochloric acid volume of positive esters of silicon acis is added in mixed liquor, then will added
Enter graphene oxide be added mixed liquor in, the positive esters of silicon acis, graphene oxide mass ratio be 1:(0.05-0.15), in 25
~30 DEG C are stirred to react 4-6 hours with 200~300 revs/min, then handle 25- in bipolar square wave high-pressure pulse electric
35min, the impulse electric field strength handled in the bipolar square wave high-pressure pulse electric is 7-13kV/cm, electrode distance 10-
15mm, frequency 100-300Hz, pulse width are 40-60 μ s;Finally ultrasonic power be 350-500W, supersonic frequency 25-
25-35min, collecting reaction product are ultrasonically treated under 45kHz;With 50~70 times of washes of absolute alcohol of reaction product weight, in
50~60 DEG C, it is 6~10 hours dry under conditions of 0.07~0.09MPa of vacuum degree, obtain Fe3O4@SiO2;
S3 is by Fe3O4@SiO2, dehydrated alcohol and water is with 1:(60~80):80 (g/mL/mL) mixing, in ultrasonic power 200
It is ultrasonically treated 15~20 minutes under conditions of~500W, 25~35kHz of supersonic frequency;Then it is added 0.17~0.2 times of water volume
Mass fraction be 28% concentrated ammonia liquor and Fe3O4@SiO2The cetyl trimethylammonium bromide that 2~3 times of weight, with 200~
300 revs/min are stirred 30~40 minutes;Continuously add 0.4~0.5 times of ammonium hydroxide volume positive esters of silicon acis and ammonium hydroxide volume 0.06~
0.07 times of 3- aminopropyl triethoxysilane adds the acid anhydrides of 3- aminopropyl triethoxysilane weight 10-30%, in 20
~30 DEG C are stirred to react 12~15 hours with 200~300 revs/min;After reaction, by reaction solution with 2000~3000 turns/
Minute centrifugation 10~15 minutes, collects bottom precipitation;Bottom precipitation is clear with 50~70 times of bottom precipitation weight of dehydrated alcohol
It washes, it is 6~10 hours dry under conditions of 40~50 DEG C, 0.07~0.09MPa of vacuum degree, obtain Fe3O4@SiO2@is mesoporous
SiO2;
S4 weighs dopamine hydrochloride and the Tris buffer of molar concentration 10mM, with solid-to-liquid ratio 1:(0.8~1.2) (mg/
ML it) mixes;Fe is then added3O4@SiO2The mesoporous SiO of@2, Fe3O4@SiO2The mesoporous SiO of@2Mass ratio with dopamine hydrochloride is
1:(4~5) are stirred to react 16~20 hours in 20~30 DEG C with 200~300 revs/min;After the reaction was completed, by reaction solution with
2000~3000 revs/min are centrifuged 10~15 minutes, collect bottom solid;By bottom solid with 50~70 times of bottom solid weight
Dehydrated alcohol and 100~200 times of bottom solid weight of water washing after, in 50~60 DEG C, 0.07~0.09MPa of vacuum degree
Under the conditions of dry 6~10 hours, obtain the Fe3O4@SiO2The mesoporous SiO of@2@PDA。
The acid anhydrides is at least one of butyl succinic anhydride, 2- methyl maleic anhydride.Further, the acid anhydrides by
Butyl succinic anhydride, 2- methyl maleic anhydride in mass ratio 1:(0.2-0.3) composition.
By in Fe3O4@SiO2Surface plate meso-porous titanium dioxide silicon layer, gained magnetic Nano material material both had magnetic material
The stalling characteristic of material, and the big specific surface area characteristic with mesoporous material, while ammonia is carried out on the surface of mesoporous silicon oxide
Base functionalization 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 invention, surfactant is not added when preparing ferroso-ferric oxide, four obtained
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, from tens nanometers to several hundred nanometers etc..And it uses
The ferroso-ferric oxide almost spherical that ethylenediamine is obtained as surfactant, surface is relatively rough, and uniform in size, particle diameter distribution is non-
It is often narrow.
The positive esters of silicon acis is tetraethyl orthosilicate and butyl silicate with mass ratio 4:The mixture of 1 composition.
The agricultural product are rice, wheat, corn, apple, banana, grape, lemon, orange, blueberry, green vegetables etc..
Compared with the existing technology, 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, comprehensive two dimensional gas chromatography mass spectrometry is modulated using solid state heat
Instrument is measured, and measurement is more rapidly, qualitative more acurrate.On the whole, the method for the present invention is quick, economical, efficiently and accurate, reduces
Adverse effect to personnel and environment.
The detection method of Residual Pesticides in Farm Produce of the present invention, compares with national standard method, has easy to operate, time-consuming
Short, organic reagent consumption is less, analysis cost is low, analysis result is more acurrate and detection limits and the more low advantage of quantitative limit.
1. using solid state heat modulation comprehensive two dimensional gas chromatography mass spectrometric hyphenated technique, sample introduction is analyzed
Standard solution preparation:Standard sample of pesticide is weighed respectively, with toluene and acetonitrile (1:1) dissolution is made into the standard of 1mg/mL
Stock solution, and it is made into according to corresponding standard items the pesticide standard working solution of various concentration.
The preparation of internal standard working solution:Weigh decafluorobiphenyl toluene and acetonitrile (1:1) dissolution is made into the standard inventory of 1mg/mL
Solution.Utilize internal standard standard reserving solution configuration toluene and acetonitrile (1:1) be made into the internal standard of 0.01mg/mL using liquid, every time into
10-200 μ L is added before sample into standard liquid or prepare liquid.
Use solid state heat modulation comprehensive two dimensional gas chromatography mass spectrometric hyphenated technique analysis pesticide standard solution and sample solution.By
1 μ L sample of automatic fluid injector sample introduction to solid state heat modulates comprehensive two dimensional gas chromatography mass spectrometer, by one-dimensional post separation
Enter the modulation column in solid-state modulator afterwards, after semiconductor refrigerating, modulation column is fast moved, and cooling material is moved to hot-zone
In be desorbed, separated into two-dimensional columns, then examined by flight time mass spectrum or level four bars mass spectrograph again
It surveys.
2. interpretation of result
By comprehensive two dimensional gas chromatography Data Analysis Software (present invention uses snow scenes science and technology Canvas software) to full 2-D data
It is handled.After reading raw mass spectrum data, software judges automatically modulation period, draws two-dimentional spectrogram;Then blob detection is carried out,
According to setting snr threshold automatic identification peak, merge the slice peak of same compound automatically, calculate final peak information automatically, wraps
Include peak height, peak width, peak area etc.;Obtain peak list.According to the Information in Mass Spectra at each peak, with NIST (NIST 17) standard spectrum library
It is compared, when similarity is greater than the set value, the automatic identification substance is completed qualitative.Be quantitatively by setting it is quantitative from
Son is completed, and quota ion is generally in mass spectrum maximum abundance fragment ion.Pass through determining for measurement various concentration standard working solution
The ratio of ion peak areas and internal standard quota ion peak area is measured, internal standard standard working curve is drawn.With standard working curve pair
Sample carries out internal standard method and completes quantitatively.Finally confirm finally by one-dimensional two-dimentional retention time and 2-3 qualitative ions.
Standard sample of pesticide is shown in Table 1 in the step (4).
Comprehensive two dimensional gas chromatography condition is in the step (4):
One-dimensional column:HP-5ms,0.25mm,0.25μm,30m
Two-dimensional columns:DB-17ms,0.18mm,0.18μm,1.2m
One-dimensional flow:1.0mL/min;Two-dimentional flow:1.0mL/min;Carrier gas:He
Shunting mode:Splitless injecting samples;Sample volume:1μL;Injector temperature:250℃;
Column oven temperature program(me):
100℃(2min)to 270℃(5min)/10℃/min
Mass Spectrometry Conditions are:
Ion source temperature:150℃;Level four bars temperature:230℃;Transmission line temperature:280℃
Scanning range:50-400amu;Scanning speed 12500amu/z (~21Hz)
Modulator condition is:
Modulate column:DV series modulations column (is suitble to C9-C40+ compound), 0.25mm
Modulator temperature:
Cold-zone:-51℃
Import hot-zone:Column oven biases -100 DEG C (minimum 40 DEG C)
Export hot-zone:Column oven biases -30 DEG C
Modulation period/release time:4s/1s.
The advantages and positive effects of the present invention are as follows:
National standard method the pesticide in vegetables and fruit is extracted it is all time-consuming and laborious, it is with high costs and secondary dirt is caused to environment
Dye carries out pre-treatment using Magnetic solid phases abstraction technique, and once-through operation is completed to extract and purifies two steps, and easy to operate,
Save trouble and labor, it is low in cost.The qualitative of common gas phase or liquid chromatogram can only rely on a retention time, full two dimension gas phase color
Spectrum increases qualitative accuracy by two retention times of one-dimensional retention time and two-dimentional retention time.Conventional one-dimensional gas phase
Chromatography chromatographic column can only be analyzed by a kind of polarity or nonpolar chromatographic column, and two-dimensional gas chromatography can be used simultaneously non-pole
Property and polar column, for the present invention using nonpolar chromatographic column as one-dimensional column, polarity chromatographic column is used as two-dimensional columns, and a variety of determinands pass through
It is first separated by molecular size when crossing one-dimensional non-polar column, using being separated again by polarity again when two-dimentional polarity chromatographic column,
Therefore the separating effect that can reach GC × GC, enables complex matrices to be efficiently separated, therefore the method for the present invention can be to complicated base
Multiple Pesticides residual progress single injected sampling is analyzed simultaneously in matter.
Jet-propelled refrigerant modulation technique need to consume a large amount of liquid nitrogen or refrigeration gas, and maintenance requirement is high, inconvenient to use.And this
The solid state heat modulation technique that invention uses is not necessarily to any refrigerant, greatly simplifies operation and maintenance process, reduces use cost, together
When can carry out long-time non-stop run, improve working efficiency.Particularly suitable for common agricultural and Agricultural Food Analysis laboratory
Daily use.
It can be according to laboratory actual conditions, using time of-flight mass spectrometer or level four bars mass spectrum.Time of-flight mass spectrometer is swept
Rate height is retouched, qualitative, quantitative is more acurrate, especially cooperates the ultra-narrow peak width of comprehensive two dimensional gas chromatography.
Detailed description of the invention
Fig. 1 is all standard specimen comprehensive two dimensional gas chromatography mass spectrograms.
Fig. 2 is actual sample comprehensive two dimensional gas chromatography mass spectrogram.
Fig. 3 is Biphenthrin actual measurement mass spectrogram and NIST comparison chart in standard solution.
Fig. 4 is Biphenthrin actual measurement mass spectrogram and NIST comparison chart in actual sample.
Specific embodiment
It is as follows using material:
Dopamine hydrochloride, No. CAS:62-31-7 is purchased from AlfaAesar (China) Chemical Co., Ltd..Molar concentration
The Tris buffer of 10mM, i.e. Tris (trishydroxymethylaminomethane) buffer of molar concentration 10mM are purchased from Nantong Runzhou
Work Co., Ltd.Polyethylene glycol, No. CAS:25322-68-3, is purchased from Shanghai Xi Long biochemical technology Co., Ltd, and molecular weight is
8000.Sodium citrate, No. CAS:6132-04-3 is purchased from this hundred full chemistries (Shanghai) Co., Ltd..Ethylenediamine, No. CAS:107-
15-3 is purchased from Shanghai Aladdin biochemical technology limited liability company.Butyl succinic anhydride, No. CAS:2035-76-9.2- methyl horse
Carry out acid anhydrides, No. CAS:616-02-4.Cetyl trimethylammonium bromide, No. CAS:57-09-0 changes purchased from AlfaAesar (China)
Learn Co., Ltd.3- aminopropyl triethoxysilane, No. CAS:919-30-2 is purchased from Chemical Industry Co., Ltd. of earth of Hangzhou.Silicic acid
Tetra-ethyl ester, No. CAS:78-10-4.Butyl silicate, No. CAS:4766-57-8.Refiner, it is more limited than bright instrument manufacturing by Shanghai
Company provides, model BILON.Vortex oscillator, by water north science popularization laboratory apparatus factory of Jintan City, model XH-C.Aoxidize stone
Black alkene is the thickness that Beijing Deco Dao Jin Science and Technology Ltd. provides:0.55-1.2nm, diameter:0.5-3 μm, the number of plies:1-5 layers
Graphene oxide.
Embodiment 1
Using Magnetic solid phases abstraction technique to the detection method of fruit, vegetable pesticide residue, include the following steps:
(1) 100g niblet refiner is homogenized 1 minute with 9500 revs/min, obtains slurries;Take 5g slurries in 50mL
In tool plug centrifuge tube, 20mL deionized water and 2mL acetonitrile is then added, is shaken 2 minutes with 1800 revs/min;
(2) 50mg magnetic Nano material is added into the tool plug centrifuge tube of step (1), continues with 1800 revs/min of concussions 4
Minute;
(3) magnet is placed in centrifuge tube side wall, magnetic Nano material sufficiently adsorbs the pesticide in agricultural product, has magnetism
Magnetic Nano material be attracted on the side wall of 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) use organic solvent 4mL to magnetic Nano material in tool plug centrifuge tube 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 analyzes prepare liquid using solid state heat modulation comprehensive two dimensional gas chromatography mass spectrometer on, before sample introduction
20 μ L of internal standard working solution is added.
The magnetic Nano material is Fe3O4@SiO2The mesoporous SiO of@2@PDA, the Fe3O4@SiO2The mesoporous SiO of@2@PDA's
Specifically synthesis process is:
S1 is by 1.35g FeCl3·6H2The mixing of O and 75mL ethylene glycol is stirred under magnetic stirring apparatus effect with 260 revs/min
It mixes 0.5 hour, 3.6g sodium acetate is then added, continue to stir 1 hour with 260 revs/min;2.2g ethylenediamine is continuously added, with
260 revs/min are stirred 15 minutes, and mixed liquor is obtained;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 is separated and collected under the action of an external magnetic field, 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
Fe3O4Nanosphere;
S2 is by 50mg Fe3O4Nanosphere is added in the hydrochloric acid of 20mL molar concentration 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 nanosphere weight is by magnetic
Property Fe3O4Nanosphere cleans up;Then by the Fe after cleaning3O4200mL ethanol/water volume ratio 4/1 is added in nanosphere
Solution adds the concentrated ammonia liquor of 2.0mL mass fraction 28%, continues under conditions of ultrasonic power 300W, supersonic frequency 25kHz
Ultrasonic treatment 20 minutes, obtains mixed liquor;Then, the positive esters of silicon acis of 1.0mL is added in mixed liquor, then graphene oxide will be added
Be added mixed liquor in, the positive esters of silicon acis, graphene oxide mass ratio be 1:0.06, it is anti-with 300 revs/min of stirrings in 28 DEG C
It answers 5 hours, then handles 30min in bipolar square wave high-pressure pulse electric, in the bipolar square wave high-pressure pulse electric
The impulse electric field strength of processing is 10kV/cm, electrode distance 15mm, frequency 200Hz, pulse width are 50 μ s;Finally exist
Ultrasonic power is 400W, supersonic frequency is ultrasonically treated 30min under being 35kHz, so that positive esters of silicon acis completes hydrolysis and polycondensation, is collected
Reaction product;By 50 times of reaction product weight of washes of absolute alcohol of reaction product, the silicon dioxide granule of blank is removed, in
50 DEG C, vacuum degree 0.07MPa vacuum drying 8 hours, obtain Fe3O4@SiO2;Wherein the positive esters of silicon acis be tetraethyl orthosilicate and
Butyl silicate is with mass ratio 4:The mixture of 1 composition;
S3 is by Fe3O4@SiO2, dehydrated alcohol and deionized water be with 1:70:80 (g/mL/mL) mixing, in ultrasonic power
It is ultrasonically treated 15 minutes under conditions of 300W, supersonic frequency 25kHz;0.17 times of deionized water volume of mass fraction is then added
For 28% concentrated ammonia liquor and Fe3O4@SiO2The cetyl trimethylammonium bromide that 3 times of weight stirs 30 points with 260 revs/min
Clock;Continuously add 0.5 times of ammonium hydroxide volume of positive esters of silicon acis and 0.07 times of ammonium hydroxide volume of 3- aminopropyl triethoxysilane, then plus
Enter the acid anhydrides of 3- aminopropyl triethoxysilane weight 15%, the acid anhydrides is pressed by butyl succinic anhydride, 2- methyl maleic anhydride
Mass ratio 1:0.25 mixes, and is stirred to react 12 hours in 25 DEG C with 300 revs/min;After reaction, by reaction solution with
2000 revs/min are centrifuged 10 minutes, collect bottom precipitation;Bottom precipitation is clear with 70 times of bottom precipitation weight of dehydrated alcohol
It washes, it is 8 hours dry under conditions of 50 DEG C, vacuum degree 0.07MPa, obtain Fe3O4@SiO2The mesoporous SiO of@2;The wherein positive silicon
Acid esters is tetraethyl orthosilicate and butyl silicate with mass ratio 4:The mixture of 1 composition;
S4 weighs 400mg dopamine hydrochloride and the Tris buffer mixing of 400mL molar concentration 10mM;Then it is added
100mg Fe3O4@SiO2The mesoporous SiO of@2, it is stirred to react 16 hours in 25 DEG C with 300 revs/min;After the reaction was completed, by reaction solution
It is centrifuged 15 minutes with 2600 revs/min, collects bottom solid;By 70 times of bottom solid weight of dehydrated alcohol of bottom solid and
It after the deionized water washing that 200 times of bottom solid weight, is dried in vacuo 10 hours, obtains described in 50 DEG C, vacuum degree 0.07MPa
Fe3O4@SiO2The mesoporous SiO of@2@PDA magnetic Nano material.
The configuration of working curve:
The standard reserving solution for taking pesticide, be each configured to be equivalent to concentration in sample be 0.01mg/kg, 0.02mg/kg,
0.05mg/kg, 0.10mg/kg, 0.50mg/kg, 1.00mg/kg, 5.00mg/kg series of tasks solution take 1.0mL respectively and add
Entering 10 μ L internal standards, with the consistent condition of sample analysis, sample introduction is analyzed using after liquid mixing.
As a result qualitative, quantitative measurement is carried out using internal mark working curve method, obtains the analysis knot of more pesticide residues in agricultural product
Fruit.
Laboratory apparatus:Gas chromatograph 7890B (Agilent);The mono- level four bars mass spectrograph (Agilent) of 5977B;Solid state heat tune
Device SSM1800 (snow scenes science and technology) processed
Comprehensive two dimensional gas chromatography condition is:
One-dimensional column:HP-5ms,0.25mm,0.25μm,30m
Two-dimensional columns:DB-17ms,0.18mm,0.18μm,1.2m
One-dimensional flow:1.0mL/min;Two-dimentional flow:1.0mL/min;Carrier gas:He
Shunting mode:Splitless injecting samples;Sample volume:1μL;Injector temperature:250℃;
Column oven temperature program(me):
100℃(2min)to 270℃(5min)/10℃/min
Mass Spectrometry Conditions are:
Ion source temperature:150℃;Level four bars temperature:230℃;Transmission line temperature:280℃
Scanning range:50-400amu;Scanning speed 12500amu/z (~21Hz)
Modulator condition is:
Modulate column:DV series modulations column, 0.25mm
Modulator temperature:
Cold-zone:-51℃
Import hot-zone:Column oven biases -100 DEG C (minimum 40 DEG C)
Export hot-zone:Column oven biases -30 DEG C
Modulation period/release time:4s/1s
The standard sample of pesticide measured is qualitative and quota ion, internal standard ion information are shown in Table 1, and the range of linearity of method adds
Mark rate of recovery index is listed in table 2.Testing result shows to detect 4 kinds of pesticides in measured agricultural product altogether, is Simanex respectively
0.23mg/kg, atrazine 0.08mg/kg, Biphenthrin 0.78mg/kg and cypermethrin 0.55mg/kg.
Table 1:Standard sample of pesticide comprehensive two dimensional gas chromatography Information in Mass Spectra
Table 2:1 line style range of embodiment, quantitative limit, recovery of standard addition result table
Embodiment 2
Substantially the same manner as Example 1, difference is only in that, the Fe3O4@SiO2The mesoporous SiO of@2@PDA's specifically synthesized
Cheng Wei:
S1 is by 1.35g FeCl3·6H2The mixing of O and 75mL ethylene glycol is stirred under magnetic stirring apparatus effect with 260 revs/min
It mixes 0.5 hour, 3.6g sodium acetate is then added, continue to stir 1 hour with 260 revs/min;2.2g ethylenediamine is continuously added, with
260 revs/min are stirred 15 minutes, and mixed liquor is obtained;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 is separated and collected under the action of an external magnetic field, 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
Fe3O4Nanosphere;
S2 is by 50mg Fe3O4Nanosphere is added in the hydrochloric acid of 20mL molar concentration 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 nanosphere weight is by magnetic
Property Fe3O4Nanosphere cleans up;Then by the Fe after cleaning3O4200mL ethanol/water volume ratio 4/1 is added in nanosphere
Solution adds the concentrated ammonia liquor of 2.0mL mass fraction 28%, continues under conditions of ultrasonic power 300W, supersonic frequency 25kHz
Ultrasonic treatment 20 minutes, obtains mixed liquor;Then, the positive esters of silicon acis of 1.0mL is added in mixed liquor, in 28 DEG C with 300 revs/min
It is stirred to react 5 hours, 30min, the bipolar square wave high-voltage pulse is then handled in bipolar square wave high-pressure pulse electric
The impulse electric field strength handled in electric field is 10kV/cm, electrode distance 15mm, frequency 200Hz, pulse width are 50 μ s;
It finally is ultrasonically treated 30min in the case where ultrasonic power is 400W, supersonic frequency is 35kHz, so that positive esters of silicon acis completes hydrolysis and contracting
It is poly-, collecting reaction product;By 50 times of reaction product weight of washes of absolute alcohol of reaction product, the silica of blank is removed
Particle is dried in vacuo 8 hours in 50 DEG C, vacuum degree 0.07MPa, obtains Fe3O4@SiO2;Wherein the positive esters of silicon acis is silicic acid four
Ethyl ester and butyl silicate are with mass ratio 4:The mixture of 1 composition;
S3 is by Fe3O4@SiO2, dehydrated alcohol and deionized water be with 1:70:80 (g/mL/mL) mixing, in ultrasonic power
It is ultrasonically treated 15 minutes under conditions of 300W, supersonic frequency 25kHz;0.17 times of deionized water volume of mass fraction is then added
For 28% concentrated ammonia liquor and Fe3O4@SiO2The cetyl trimethylammonium bromide that 3 times of weight stirs 30 points with 260 revs/min
Clock;Continuously add 0.5 times of ammonium hydroxide volume of positive esters of silicon acis and 0.07 times of ammonium hydroxide volume of 3- aminopropyl triethoxysilane, then plus
Enter the acid anhydrides of 3- aminopropyl triethoxysilane weight 15%, the acid anhydrides is pressed by butyl succinic anhydride, 2- methyl maleic anhydride
Mass ratio 1:0.25 mixes, and is stirred to react 12 hours in 25 DEG C with 300 revs/min;After reaction, by reaction solution with
2000 revs/min are centrifuged 10 minutes, collect bottom precipitation;Bottom precipitation is clear with 70 times of bottom precipitation weight of dehydrated alcohol
It washes, it is 8 hours dry under conditions of 50 DEG C, vacuum degree 0.07MPa, obtain Fe3O4@SiO2The mesoporous SiO of@2;The wherein positive silicon
Acid esters is tetraethyl orthosilicate and butyl silicate with mass ratio 4:The mixture of 1 composition;
S4 weighs 400mg dopamine hydrochloride and the Tris buffer mixing of 400mL molar concentration 10mM;Then it is added
100mg Fe3O4@SiO2The mesoporous SiO of@2, it is stirred to react 16 hours in 25 DEG C with 300 revs/min;After the reaction was completed, by reaction solution
It is centrifuged 15 minutes with 2600 revs/min, collects bottom solid;By 70 times of bottom solid weight of dehydrated alcohol of bottom solid and
It after the deionized water washing that 200 times of bottom solid weight, is dried in vacuo 10 hours, obtains described in 50 DEG C, vacuum degree 0.07MPa
Fe3O4@SiO2The mesoporous SiO of@2@PDA magnetic Nano material.
Table 3:2 line style range of embodiment, quantitative limit, recovery of standard addition result table
Embodiment 3
Substantially the same manner as Example 1, difference is only in that, the Fe3O4@SiO2The mesoporous SiO of@2@PDA's specifically synthesized
Cheng Wei:
S1 is by 1.35g FeCl3·6H2The mixing of O and 75mL ethylene glycol is stirred under magnetic stirring apparatus effect with 260 revs/min
It mixes 0.5 hour, 3.6g sodium acetate is then added, continue to stir 1 hour with 260 revs/min;2.2g ethylenediamine is continuously added, with
260 revs/min are stirred 15 minutes, and mixed liquor is obtained;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 is separated and collected under the action of an external magnetic field, 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
Fe3O4Nanosphere;
S2 is by 50mg Fe3O4Nanosphere is added in the hydrochloric acid of 20mL molar concentration 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 nanosphere weight is by magnetic
Property Fe3O4Nanosphere cleans up;Then by the Fe after cleaning3O4200mL ethanol/water volume ratio 4/1 is added in nanosphere
Solution adds the concentrated ammonia liquor of 2.0mL mass fraction 28%, continues under conditions of ultrasonic power 300W, supersonic frequency 25kHz
Ultrasonic treatment 20 minutes, obtains mixed liquor;Then, the positive esters of silicon acis of 1.0mL is added in mixed liquor, then graphene oxide will be added
Be added mixed liquor in, the positive esters of silicon acis, graphene oxide mass ratio be 1:0.06, it is anti-with 300 revs/min of stirrings in 28 DEG C
It answers 5 hours, then handles 60min in bipolar square wave high-pressure pulse electric, in the bipolar square wave high-pressure pulse electric
The impulse electric field strength of processing is 10kV/cm, electrode distance 15mm, frequency 200Hz, pulse width are 50 μ s, so that just
Esters of silicon acis completes hydrolysis and polycondensation, collecting reaction product;By 50 times of reaction product weight of washes of absolute alcohol of reaction product,
The silicon dioxide granule for removing blank is dried in vacuo 8 hours in 50 DEG C, vacuum degree 0.07MPa, obtains Fe3O4@SiO2;Wherein institute
Stating positive esters of silicon acis is tetraethyl orthosilicate and butyl silicate with mass ratio 4:The mixture of 1 composition;
S3 is by Fe3O4@SiO2, dehydrated alcohol and deionized water be with 1:70:80 (g/mL/mL) mixing, in ultrasonic power
It is ultrasonically treated 15 minutes under conditions of 300W, supersonic frequency 25kHz;0.17 times of deionized water volume of mass fraction is then added
For 28% concentrated ammonia liquor and Fe3O4@SiO2The cetyl trimethylammonium bromide that 3 times of weight stirs 30 points with 260 revs/min
Clock;Continuously add 0.5 times of ammonium hydroxide volume of positive esters of silicon acis and 0.07 times of ammonium hydroxide volume of 3- aminopropyl triethoxysilane, then plus
Enter the acid anhydrides of 3- aminopropyl triethoxysilane weight 15%, the acid anhydrides is pressed by butyl succinic anhydride, 2- methyl maleic anhydride
Mass ratio 1:0.25 mixes, and is stirred to react 12 hours in 25 DEG C with 300 revs/min;After reaction, by reaction solution with
2000 revs/min are centrifuged 10 minutes, collect bottom precipitation;Bottom precipitation is clear with 70 times of bottom precipitation weight of dehydrated alcohol
It washes, it is 8 hours dry under conditions of 50 DEG C, vacuum degree 0.07MPa, obtain Fe3O4@SiO2The mesoporous SiO of@2;The wherein positive silicon
Acid esters is tetraethyl orthosilicate and butyl silicate with mass ratio 4:The mixture of 1 composition;
S4 weighs 400mg dopamine hydrochloride and the Tris buffer mixing of 400mL molar concentration 10mM;Then it is added
100mg Fe3O4@SiO2The mesoporous SiO of@2, it is stirred to react 16 hours in 25 DEG C with 300 revs/min;After the reaction was completed, by reaction solution
It is centrifuged 15 minutes with 2600 revs/min, collects bottom solid;By 70 times of bottom solid weight of dehydrated alcohol of bottom solid and
It after the deionized water washing that 200 times of bottom solid weight, is dried in vacuo 10 hours, obtains described in 50 DEG C, vacuum degree 0.07MPa
Fe3O4@SiO2The mesoporous SiO of@2@PDA magnetic Nano material.
Table 4:3 line style range of embodiment, quantitative limit, recovery of standard addition result table
Embodiment 4
Substantially the same manner as Example 1, difference is only in that, the Fe3O4@SiO2The mesoporous SiO of@2@PDA's specifically synthesized
Cheng Wei:
S1 is by 1.35g FeCl3·6H2The mixing of O and 75mL ethylene glycol is stirred under magnetic stirring apparatus effect with 260 revs/min
It mixes 0.5 hour, 3.6g sodium acetate is then added, continue to stir 1 hour with 260 revs/min;2.2g ethylenediamine is continuously added, with
260 revs/min are stirred 15 minutes, and mixed liquor is obtained;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 is separated and collected under the action of an external magnetic field, 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
Fe3O4Nanosphere;
S2 is by 50mg Fe3O4Nanosphere is added in the hydrochloric acid of 20mL molar concentration 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 nanosphere weight is by magnetic
Property Fe3O4Nanosphere cleans up;Then by the Fe after cleaning3O4200mL ethanol/water volume ratio 4/1 is added in nanosphere
Solution adds the concentrated ammonia liquor of 2.0mL mass fraction 28%, continues under conditions of ultrasonic power 300W, supersonic frequency 25kHz
Ultrasonic treatment 20 minutes, obtains mixed liquor;Then, the positive esters of silicon acis of 1.0mL is added in mixed liquor, then graphene oxide will be added
Be added mixed liquor in, the positive esters of silicon acis, graphene oxide mass ratio be 1:0.06, it is anti-with 300 revs/min of stirrings in 28 DEG C
It answers 5 hours, is then ultrasonically treated 60min in the case where ultrasonic power is 400W, supersonic frequency is 35kHz, so that positive esters of silicon acis is completed
Hydrolysis and polycondensation, collecting reaction product;By 50 times of reaction product weight of washes of absolute alcohol of reaction product, blank is removed
Silicon dioxide granule is dried in vacuo 8 hours in 50 DEG C, vacuum degree 0.07MPa, obtains Fe3O4@SiO2;The wherein positive esters of silicon acis
It is tetraethyl orthosilicate and butyl silicate with mass ratio 4:The mixture of 1 composition;
S3 is by Fe3O4@SiO2, dehydrated alcohol and deionized water be with 1:70:80 (g/mL/mL) mixing, in ultrasonic power
It is ultrasonically treated 15 minutes under conditions of 300W, supersonic frequency 25kHz;0.17 times of deionized water volume of mass fraction is then added
For 28% concentrated ammonia liquor and Fe3O4@SiO2The cetyl trimethylammonium bromide that 3 times of weight stirs 30 points with 260 revs/min
Clock;Continuously add 0.5 times of ammonium hydroxide volume of positive esters of silicon acis and 0.07 times of ammonium hydroxide volume of 3- aminopropyl triethoxysilane, then plus
Enter the acid anhydrides of 3- aminopropyl triethoxysilane weight 15%, the acid anhydrides is pressed by butyl succinic anhydride, 2- methyl maleic anhydride
Mass ratio 1:0.25 mixes, and is stirred to react 12 hours in 25 DEG C with 300 revs/min;After reaction, by reaction solution with
2000 revs/min are centrifuged 10 minutes, collect bottom precipitation;Bottom precipitation is clear with 70 times of bottom precipitation weight of dehydrated alcohol
It washes, it is 8 hours dry under conditions of 50 DEG C, vacuum degree 0.07MPa, obtain Fe3O4@SiO2The mesoporous SiO of@2;The wherein positive silicon
Acid esters is tetraethyl orthosilicate and butyl silicate with mass ratio 4:The mixture of 1 composition;
S4 weighs 400mg dopamine hydrochloride and the Tris buffer mixing of 400mL molar concentration 10mM;Then it is added
100mg Fe3O4@SiO2The mesoporous SiO of@2, it is stirred to react 16 hours in 25 DEG C with 300 revs/min;After the reaction was completed, by reaction solution
It is centrifuged 15 minutes with 2600 revs/min, collects bottom solid;By 70 times of bottom solid weight of dehydrated alcohol of bottom solid and
It after the deionized water washing that 200 times of bottom solid weight, is dried in vacuo 10 hours, obtains described in 50 DEG C, vacuum degree 0.07MPa
Fe3O4@SiO2The mesoporous SiO of@2@PDA magnetic Nano material.
Table 5:4 line style range of embodiment, quantitative limit, recovery of standard addition result table
Embodiment 5
Substantially the same manner as Example 1, difference is only in that, the Fe3O4@SiO2The mesoporous SiO of@2@PDA's specifically synthesized
Cheng Wei:
S1 is by 1.35g FeCl3·6H2The mixing of O and 75mL ethylene glycol is stirred under magnetic stirring apparatus effect with 260 revs/min
It mixes 0.5 hour, 3.6g sodium acetate is then added, continue to stir 1 hour with 260 revs/min;2.2g ethylenediamine is continuously added, with
260 revs/min are stirred 15 minutes, and mixed liquor is obtained;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 is separated and collected under the action of an external magnetic field, 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
Fe3O4Nanosphere;
S2 is by 50mg Fe3O4Nanosphere is added in the hydrochloric acid of 20mL molar concentration 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 nanosphere weight is by magnetic
Property Fe3O4Nanosphere cleans up;Then by the Fe after cleaning3O4200mL ethanol/water volume ratio 4/1 is added in nanosphere
Solution adds the concentrated ammonia liquor of 2.0mL mass fraction 28%, continues under conditions of ultrasonic power 300W, supersonic frequency 25kHz
Ultrasonic treatment 20 minutes, obtains mixed liquor;Then, the positive esters of silicon acis of 1.0mL is added in mixed liquor, then graphene oxide will be added
Be added mixed liquor in, the positive esters of silicon acis, graphene oxide mass ratio be 1:0.06, it is anti-with 300 revs/min of stirrings in 28 DEG C
It answers 5 hours, then handles 30min in bipolar square wave high-pressure pulse electric, in the bipolar square wave high-pressure pulse electric
The impulse electric field strength of processing is 10kV/cm, electrode distance 15mm, frequency 200Hz, pulse width are 50 μ s;Finally exist
Ultrasonic power is 400W, supersonic frequency is ultrasonically treated 30min under being 35kHz, so that positive esters of silicon acis completes hydrolysis and polycondensation, is collected
Reaction product;By 50 times of reaction product weight of washes of absolute alcohol of reaction product, the silicon dioxide granule of blank is removed, in
50 DEG C, vacuum degree 0.07MPa vacuum drying 8 hours, obtain Fe3O4@SiO2;Wherein the positive esters of silicon acis be tetraethyl orthosilicate and
Butyl silicate is with mass ratio 4:The mixture of 1 composition;
S3 is by Fe3O4@SiO2, dehydrated alcohol and deionized water be with 1:70:80 (g/mL/mL) mixing, in ultrasonic power
It is ultrasonically treated 15 minutes under conditions of 300W, supersonic frequency 25kHz;0.17 times of deionized water volume of mass fraction is then added
For 28% concentrated ammonia liquor and Fe3O4@SiO2The cetyl trimethylammonium bromide that 3 times of weight stirs 30 points with 260 revs/min
Clock;Continuously add 0.5 times of ammonium hydroxide volume of positive esters of silicon acis and 0.07 times of ammonium hydroxide volume of 3- aminopropyl triethoxysilane, then plus
Enter the acid anhydrides of 3- aminopropyl triethoxysilane weight 15%, the acid anhydrides is butyl succinic anhydride, in 25 DEG C with 300 revs/min
Clock is stirred to react 12 hours;After reaction, reaction solution is centrifuged 10 minutes with 2000 revs/min, collects bottom precipitation;The bottom of by
70 times of bottom precipitation weight of washes of absolute alcohol of portion's precipitating, it is 8 hours dry under conditions of 50 DEG C, vacuum degree 0.07MPa,
Obtain Fe3O4@SiO2The mesoporous SiO of@2;Wherein the positive esters of silicon acis is tetraethyl orthosilicate and butyl silicate with mass ratio 4:1 group
At mixture;
S4 weighs 400mg dopamine hydrochloride and the Tris buffer mixing of 400mL molar concentration 10mM;Then it is added
100mg Fe3O4@SiO2The mesoporous SiO of@2, it is stirred to react 16 hours in 25 DEG C with 300 revs/min;After the reaction was completed, by reaction solution
It is centrifuged 15 minutes with 2600 revs/min, collects bottom solid;By 70 times of bottom solid weight of dehydrated alcohol of bottom solid and
It after the deionized water washing that 200 times of bottom solid weight, is dried in vacuo 10 hours, obtains described in 50 DEG C, vacuum degree 0.07MPa
Fe3O4@SiO2The mesoporous SiO of@2@PDA magnetic Nano material.
Table 6:5 line style range of embodiment, quantitative limit, recovery of standard addition result table
Embodiment 6
Substantially the same manner as Example 1, difference is only in that, the Fe3O4@SiO2The mesoporous SiO of@2@PDA's specifically synthesized
Cheng Wei:
S1 is by 1.35g FeCl3·6H2The mixing of O and 75mL ethylene glycol is stirred under magnetic stirring apparatus effect with 260 revs/min
It mixes 0.5 hour, 3.6g sodium acetate is then added, continue to stir 1 hour with 260 revs/min;2.2g ethylenediamine is continuously added, with
260 revs/min are stirred 15 minutes, and mixed liquor is obtained;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 is separated and collected under the action of an external magnetic field, 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
Fe3O4Nanosphere;
S2 is by 50mg Fe3O4Nanosphere is added in the hydrochloric acid of 20mL molar concentration 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 nanosphere weight is by magnetic
Property Fe3O4Nanosphere cleans up;Then by the Fe after cleaning3O4200mL ethanol/water volume ratio 4/1 is added in nanosphere
Solution adds the concentrated ammonia liquor of 2.0mL mass fraction 28%, continues under conditions of ultrasonic power 300W, supersonic frequency 25kHz
Ultrasonic treatment 20 minutes, obtains mixed liquor;Then, the positive esters of silicon acis of 1.0mL is added in mixed liquor, then graphene oxide will be added
Be added mixed liquor in, the positive esters of silicon acis, graphene oxide mass ratio be 1:0.06, it is anti-with 300 revs/min of stirrings in 28 DEG C
It answers 5 hours, then handles 30min in bipolar square wave high-pressure pulse electric, in the bipolar square wave high-pressure pulse electric
The impulse electric field strength of processing is 10kV/cm, electrode distance 15mm, frequency 200Hz, pulse width are 50 μ s;Finally exist
Ultrasonic power is 400W, supersonic frequency is ultrasonically treated 30min under being 35kHz, so that positive esters of silicon acis completes hydrolysis and polycondensation, is collected
Reaction product;By 50 times of reaction product weight of washes of absolute alcohol of reaction product, the silicon dioxide granule of blank is removed, in
50 DEG C, vacuum degree 0.07MPa vacuum drying 8 hours, obtain Fe3O4@SiO2;Wherein the positive esters of silicon acis be tetraethyl orthosilicate and
Butyl silicate is with mass ratio 4:The mixture of 1 composition;
S3 is by Fe3O4@SiO2, dehydrated alcohol and deionized water be with 1:70:80 (g/mL/mL) mixing, in ultrasonic power
It is ultrasonically treated 15 minutes under conditions of 300W, supersonic frequency 25kHz;0.17 times of deionized water volume of mass fraction is then added
For 28% concentrated ammonia liquor and Fe3O4@SiO2The cetyl trimethylammonium bromide that 3 times of weight stirs 30 points with 260 revs/min
Clock;Continuously add 0.5 times of ammonium hydroxide volume of positive esters of silicon acis and 0.07 times of ammonium hydroxide volume of 3- aminopropyl triethoxysilane, then plus
Enter the acid anhydrides of 3- aminopropyl triethoxysilane weight 15%, the acid anhydrides is 2- methyl maleic anhydride, in 25 DEG C with 300 turns/
Minute is stirred to react 12 hours;After reaction, reaction solution is centrifuged 10 minutes with 2000 revs/min, collects bottom precipitation;It will
70 times of bottom precipitation weight of washes of absolute alcohol of bottom precipitation, dry 8 is small under conditions of 50 DEG C, vacuum degree 0.07MPa
When, obtain Fe3O4@SiO2The mesoporous SiO of@2;Wherein the positive esters of silicon acis is tetraethyl orthosilicate and butyl silicate with mass ratio 4:1
The mixture of composition;
S4 weighs 400mg dopamine hydrochloride and the Tris buffer mixing of 400mL molar concentration 10mM;Then it is added
100mg Fe3O4@SiO2The mesoporous SiO of@2, it is stirred to react 16 hours in 25 DEG C with 300 revs/min;After the reaction was completed, by reaction solution
It is centrifuged 15 minutes with 2600 revs/min, collects bottom solid;By 70 times of bottom solid weight of dehydrated alcohol of bottom solid and
It after the deionized water washing that 200 times of bottom solid weight, is dried in vacuo 10 hours, obtains described in 50 DEG C, vacuum degree 0.07MPa
Fe3O4@SiO2The mesoporous SiO of@2@PDA magnetic Nano material.
Table 7:6 line style range of embodiment, quantitative limit, recovery of standard addition result table
Claims (10)
1. it is a kind of using Magnetic solid phases abstraction technique to the detection method of fruit, vegetable pesticide residue, which is characterized in that including such as
Lower step:
(1) agricultural product are homogenized with refiner, water is added and acetonitrile is dispersed;
(2) investment magnetic Nano material carries out continuous concussion extraction;
(3) magnetic Nano material of extraction absorption pesticide is separated 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 solid state heat modulation comprehensive two dimensional gas chromatography mass spectrometer.
2. special as described in claim 1 using Magnetic solid phases abstraction technique to the detection method of fruit, vegetable pesticide residue
Sign is, is made of following step:
(1) 100~150g agricultural product are homogenized with refiner, obtain slurries;It takes 5~15g slurries to have in 20~80mL to fill in
In centrifuge tube, 15~40mL water and 1~3mL acetonitrile is then added, shakes 2~6 minutes;
(2) 50~150mg magnetic Nano material is added into the tool plug centrifuge tube of step (1), continues concussion 3~9 minutes;
(3) magnet is placed in centrifuge tube side wall, magnetic Nano material sufficiently adsorbs the pesticide in agricultural product, has magnetic magnetic
Property nano material is attracted on the side wall of near magnet, the mixed liquor of agricultural product, acetonitrile and water is discarded, with water to magnetic Nano
Material clean 2~3 times, discard cleaning solution;
(4) magnetic Nano material ultrasound in tool plug centrifuge tube is eluted 3~9 minutes using 2~5mL of organic solvent, magnetic Nano
The pesticide of particle absorption is eluted in organic solvent, obtains eluent;Then eluent is concentrated into 0.8 using nitrogen evaporator~
1.2mL, filtering, obtains prepare liquid;
(5) machine analyzes prepare liquid using solid state heat modulation comprehensive two dimensional gas chromatography mass spectrometer on, is added before sample introduction
Internal standard working solution carries out qualitative, quantitative measurement using internal mark working curve method, obtains the analysis knot of more pesticide residues in agricultural product
Fruit.
3. as claimed in claim 1 or 2 using Magnetic solid phases abstraction technique to the detection method of fruit, vegetable pesticide residue,
It is characterized in that, organic solvent described in step (4) is acetonitrile and methanol with volume ratio (3~4):The mixed solvent of 1 composition.
4. as claimed in claim 1 or 2 using Magnetic solid phases abstraction technique to the detection method of fruit, vegetable pesticide residue,
It is characterized in that, the water consumption for cleaning magnetic Nano material in step (3) every time is 2~5mL.
5. as claimed in claim 1 or 2 using Magnetic solid phases abstraction technique to the detection method of fruit, vegetable pesticide residue,
It is characterized in that, magnetic Nano material described in step (2) is Fe3O4@SiO2@PDA。
6. as claimed in claim 1 or 2 using Magnetic solid phases abstraction technique to the detection method of fruit, vegetable pesticide residue,
It is characterized in that, magnetic Nano material described in step (2) is Fe3O4@SiO2The mesoporous SiO of@2@PDA。
7. special as claimed in claim 5 using Magnetic solid phases abstraction technique to the detection method of fruit, vegetable pesticide residue
Sign is, the Fe3O4@SiO2The specific synthesis process of@PDA is:
S1 is by FeCl3·6H2O and ethylene glycol are with solid-to-liquid ratio 1:(50~60) (g/mL) mixing, with 200 under magnetic agitation effect
~300 revs/min are stirred 0.5~1 hour, and FeCl is then added3·6H2The 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, and mixed liquor is obtained;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 is separated and collected under the action of an external magnetic field, 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 Fe3O4Nanosphere;
S2 is by Fe3O4Nanosphere 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
The water that 80~200 times of microspheres weight is by Fe3O4Nanosphere cleans up;Then by the Fe after cleaning3O4Salt is added in nanosphere
The mixed solution of the ethanol/water volume ratio 4/1 of 8~12 times of sour volume adds 0.09~0.1 times of hydrochloric acid volume of mass fraction
28% concentrated ammonia liquor continues to be ultrasonically treated 10~30 under conditions of 200~500W of ultrasonic power, 25~35kHz of supersonic frequency
Minute, obtain mixed liquor;Then, 0.04~0.05 times of hydrochloric acid volume of positive esters of silicon acis is added in mixed liquor, in 25~30 DEG C
5~7 hours are stirred to react with 200~300 revs/min, collecting reaction product;With 50~70 times of reaction product weight of anhydrous second
Alcohol cleaning, it is 6~10 hours dry under conditions of 50~60 DEG C, 0.07~0.09MPa of vacuum degree, obtain Fe3O4@SiO2;
S3 weighs dopamine hydrochloride and the Tris buffer of molar concentration 10mM, with solid-to-liquid ratio 1:(0.8~1.2) (mg/mL)
Mixing;Fe is then added3O4@SiO2, Fe3O4@SiO2Mass ratio with dopamine hydrochloride is 1:(4~5), in 20~30 DEG C with
200~300 revs/min are stirred to react 16~20 hours;After the reaction was completed, reaction solution is centrifuged with 2000~3000 revs/min
10~15 minutes, collect bottom solid;By bottom solid with 50~70 times of bottom solid weight of dehydrated alcohol and bottom solid
It is 6~10 hours dry under conditions of 50~60 DEG C, 0.07~0.09MPa of vacuum degree after the water washing that 100~200 times of weight,
Obtain the Fe3O4@SiO2@PDA。
8. special as claimed in claim 6 using Magnetic solid phases abstraction technique to the detection method of fruit, vegetable pesticide residue
Sign is, the Fe3O4@SiO2The mesoporous SiO of@2The specific synthesis process of@PDA is:
S1 is by FeCl3·6H2O and ethylene glycol are with solid-to-liquid ratio 1:(50~60) (g/mL) mixing, with 200 under magnetic agitation effect
~300 revs/min are stirred 0.5~1 hour, and FeCl is then added3·6H2The 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, and mixed liquor is obtained;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 is separated and collected under the action of an external magnetic field, 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 Fe3O4Nanosphere;
S2 is by Fe3O4Nanosphere 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 water that 80~200 times of ball weight is by Fe3O4Nanosphere cleans up;Then by the Fe after cleaning3O4Hydrochloric acid is added in nanosphere
The mixed solution of 8~12 times of volume of ethanol/water volume ratio 4/1 adds 0.09~0.1 times of hydrochloric acid volume of mass fraction
28% concentrated ammonia liquor continues to be ultrasonically treated 10~30 under conditions of 200~500W of ultrasonic power, 25~35kHz of supersonic frequency
Minute, obtain mixed liquor;Then, 0.04~0.05 times of hydrochloric acid volume of positive esters of silicon acis is added in mixed liquor, in 25~30 DEG C
5~7 hours are stirred to react with 200~300 revs/min, collecting reaction product;With 50~70 times of reaction product weight of anhydrous second
Alcohol cleaning, it is 6~10 hours dry under conditions of 50~60 DEG C, 0.07~0.09MPa of vacuum degree, obtain Fe3O4@SiO2;
S3 is by Fe3O4@SiO2, dehydrated alcohol and water is with 1:(60~80):80 (g/mL/mL) mixing, ultrasonic power 200~
It is ultrasonically treated 15~20 minutes under conditions of 500W, 25~35kHz of supersonic frequency;Then it is added 0.17~0.2 times of water volume
The concentrated ammonia liquor and Fe that mass fraction is 28%3O4@SiO2The cetyl trimethylammonium bromide that 2~3 times of weight, with 200~300
Rev/min stirring 30~40 minutes;Continuously add 0.4~0.5 times of ammonium hydroxide volume positive esters of silicon acis and ammonium hydroxide volume 0.06~
0.07 times of 3- aminopropyl triethoxysilane is stirred to react 12~15 hours in 20~30 DEG C with 200~300 revs/min;Instead
After answering, reaction solution is centrifuged 10~15 minutes with 2000~3000 revs/min, collects bottom precipitation;Bottom precipitation is used
The washes of absolute alcohol that 50~70 times of bottom precipitation weight, it is dry under conditions of 40~50 DEG C, 0.07~0.09MPa of vacuum degree
6~10 hours, obtain Fe3O4@SiO2The mesoporous SiO of@2;
S4 weighs dopamine hydrochloride and the Tris buffer of molar concentration 10mM, with solid-to-liquid ratio 1:(0.8~1.2) (mg/mL)
Mixing;Fe is then added3O4@SiO2The mesoporous SiO of@2, Fe3O4@SiO2The mesoporous SiO of@2Mass ratio with dopamine hydrochloride is 1:(4
~5) it, is stirred to react 16~20 hours in 20~30 DEG C with 200~300 revs/min;After the reaction was completed, by reaction solution with 2000
~3000 revs/min are centrifuged 10~15 minutes, collect bottom solid;By 50~70 times of bottom solid weight of nothing of bottom solid
After water-ethanol and 100~200 times of bottom solid weight of water washing, in 50~60 DEG C, the condition of 0.07~0.09MPa of vacuum degree
Lower drying 6~10 hours, obtains the Fe3O4@SiO2The mesoporous SiO of@2@PDA。
9. special as claimed in claim 6 using Magnetic solid phases abstraction technique to the detection method of fruit, vegetable pesticide residue
Sign is, the Fe3O4@SiO2The mesoporous SiO of@2The specific synthesis process of@PDA is:
S1 is by FeCl3·6H2O and ethylene glycol are with solid-to-liquid ratio 1:(50~60) (g/mL) mixing, with 200 under magnetic agitation effect
~300 revs/min are stirred 0.5~1 hour, and FeCl is then added3·6H2The 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, and mixed liquor is obtained;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 is separated and collected under the action of an external magnetic field, 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 Fe3O4Nanosphere;
S2 is by Fe3O4Nanosphere 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 water that 80~200 times of ball weight is by Fe3O4Nanosphere cleans up;Then by the Fe after cleaning3O4Hydrochloric acid is added in nanosphere
The mixed solution of 8~12 times of volume of ethanol/water volume ratio 4/1 adds 0.09~0.1 times of hydrochloric acid volume of mass fraction
28% concentrated ammonia liquor continues to be ultrasonically treated 10~30 under conditions of 200~500W of ultrasonic power, 25~35kHz of supersonic frequency
Minute, obtain mixed liquor;Then, 0.04~0.05 times of hydrochloric acid volume of positive esters of silicon acis is added in mixed liquor, then oxygen will be added
Graphite alkene be added mixed liquor in, the positive esters of silicon acis, graphene oxide mass ratio be 1:(0.05-0.15), in 25~30
It DEG C is stirred to react 4-6 hours with 200~300 revs/min, then handles 25- in bipolar square wave high-pressure pulse electric
35min, the impulse electric field strength handled in the bipolar square wave high-pressure pulse electric is 7-13kV/cm, electrode distance 10-
15mm, frequency 100-300Hz, pulse width are 40-60 μ s;Finally ultrasonic power be 350-500W, supersonic frequency 25-
25-35min, collecting reaction product are ultrasonically treated under 45kHz;With 50~70 times of washes of absolute alcohol of reaction product weight, in
50~60 DEG C, it is 6~10 hours dry under conditions of 0.07~0.09MPa of vacuum degree, obtain Fe3O4@SiO2;
S3 is by Fe3O4@SiO2, dehydrated alcohol and water is with 1:(60~80):80 (g/mL/mL) mixing, ultrasonic power 200~
It is ultrasonically treated 15~20 minutes under conditions of 500W, 25~35kHz of supersonic frequency;Then it is added 0.17~0.2 times of water volume
The concentrated ammonia liquor and Fe that mass fraction is 28%3O4@SiO2The cetyl trimethylammonium bromide that 2~3 times of weight, with 200~300
Rev/min stirring 30~40 minutes;Continuously add 0.4~0.5 times of ammonium hydroxide volume positive esters of silicon acis and ammonium hydroxide volume 0.06~
0.07 times of 3- aminopropyl triethoxysilane adds the acid anhydrides of 3- aminopropyl triethoxysilane weight 10-30%, in 20
~30 DEG C are stirred to react 12~15 hours with 200~300 revs/min;After reaction, by reaction solution with 2000~3000 turns/
Minute centrifugation 10~15 minutes, collects bottom precipitation;Bottom precipitation is clear with 50~70 times of bottom precipitation weight of dehydrated alcohol
It washes, it is 6~10 hours dry under conditions of 40~50 DEG C, 0.07~0.09MPa of vacuum degree, obtain Fe3O4@SiO2@is mesoporous
SiO2;The acid anhydrides is at least one of butyl succinic anhydride, 2- methyl maleic anhydride;
S4 weighs dopamine hydrochloride and the Tris buffer of molar concentration 10mM, with solid-to-liquid ratio 1:(0.8~1.2) (mg/mL)
Mixing;Fe is then added3O4@SiO2The mesoporous SiO of@2, Fe3O4@SiO2The mesoporous SiO of@2Mass ratio with dopamine hydrochloride is 1:(4
~5) it, is stirred to react 16~20 hours in 20~30 DEG C with 200~300 revs/min;After the reaction was completed, by reaction solution with 2000
~3000 revs/min are centrifuged 10~15 minutes, collect bottom solid;By 50~70 times of bottom solid weight of nothing of bottom solid
After water-ethanol and 100~200 times of bottom solid weight of water washing, in 50~60 DEG C, the condition of 0.07~0.09MPa of vacuum degree
Lower drying 6~10 hours, obtains the Fe3O4@SiO2The mesoporous SiO of@2@PDA。
10. as claimed in claim 9 using Magnetic solid phases abstraction technique to the detection method of fruit, vegetable pesticide residue,
It is characterized in that, the surfactant is one or more of polyethylene glycol, sodium citrate, ethylenediamine;The positive esters of silicon acis
It is tetraethyl orthosilicate and butyl silicate with mass ratio 4:The mixture of 1 composition.
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CN114042440A (en) * | 2021-09-17 | 2022-02-15 | 中国药科大学 | Magnetic solid phase extraction adsorbent, preparation method and application |
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