CN107894484A - The quick determination method that Multiple Pesticides remain in a kind of blueberry - Google Patents
The quick determination method that Multiple Pesticides remain in a kind of blueberry Download PDFInfo
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- CN107894484A CN107894484A CN201711030306.1A CN201711030306A CN107894484A CN 107894484 A CN107894484 A CN 107894484A CN 201711030306 A CN201711030306 A CN 201711030306A CN 107894484 A CN107894484 A CN 107894484A
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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Abstract
The invention discloses the quick determination method that Multiple Pesticides in a kind of blueberry remain, it is made up of following step：(1) Blueberry is homogenized with refiner, adds suitable quantity of water and acetonitrile is disperseed；(2) appropriate magnetic metal organic framework materials are put into and carry out continuous concussion extraction；(3) the magnetic metal organic framework materials for having been adsorbed agricultural chemicals to extraction using magnet are separated from blueberry solution；(4) the magnetic metal organic framework materials for having adsorbed agricultural chemicals are eluted using a small amount of organic reagent；(5) analysis detection is carried out to elution solution using gas chromatograph/mass spectrometer.The method applied in the present invention has that the operating time is short, and organic reagent consumption is few, the advantages such as analysis cost is low.
Description
Technical field
The present invention relates to technical field of analysis and detection, and in particular to the quick detection side that Multiple Pesticides remain in a kind of blueberry
Method.
Background technology
Blueberry, English name：Blueberry, blue berry is meant, belong to Ericaceae, cowberry platymiscium.Originating from north
U.S., perennial shrub small berries fruit tree.Cause and effect is in blueness in fact, therefore referred to as blueberry.The cowberry platymiscium of whole world distribution is up to 400
Remaining kind, main product are otherwise known as American blueberry in the U.S..China's wild blueberry is mainly produced in Changbai Mountain, Daxing'an Mountainrange and the Xiaoxinanlin Mountains
Forest zone, and it is most of in Daxinganling District.Domestication's cultivation is just successfully carried out in recent years.Research of the China to blueberry is begun
In in the early 1980s, be to be taken the lead in entering blueberry research field by small berries research institute of Jilin Agriculture University, and first is built
Blueberry industry production base is stood.Blueberry is a kind of small berries, and fruit is beautiful, blue by 1 layer of white fruit powder in blueness, color and luster
Parcel, pulp is fine and smooth, seed is minimum.Blueberry averagely weighs 0.5~2.5g, and 5g, fruit colour are beautiful, pleasing, blue again for maximum
Color and by 1 layer of white fruit powder, pulp is fine and smooth, and seed is minimum, edible rate 100%, has light fragrance, sweet and sour palatability, is one fresh
Eat good merchantable brand.In Blueberry in addition to the sugar, acid and Vc of routine, rich in VE, VA, VB, SOD, ursin, protein, anthocyanin,
The mineral element such as dietary fibre and abundant K, Fe, Zn, Ca.Blueberry has extremely strong medical value and nutrition and health care work(
Can, international food and agricultural organization is classified as one of five big healthy food of the mankind.Containing abundant nutritional ingredient in Blueberry, have
The function such as prevent cranial nerve aging, protection eyesight, cardiac stimulant, anticancer, softening blood vessel, enhancing human organism immune；Wherein, due to blueberry
Rich in anthocyanidin, there is activation retina effect, eyesight can be strengthened, prevent eyeball fatigue and enjoy and gaze at.And according to the U.S.,
Japan, European Section scholar research, often edible blueberry product, can also significantly strengthen eyesight, anti-eye strain.Clinical medicine
Report displays that the anthocyanidin in blueberry can promote the visual purple in retina cell to regenerate, pre- myopia prevention, promotes eyesight.
Blueberry is referred to as " fruit queen " and " king of berry ", possesses very high economic value, therefore extensively blue or green by peasant
Look at.But blueberry in growth course because pest and disease damage is more, in order to improve yield, obtain higher income, in production may be used
The agricultural chemicals of application reaches hundreds of, and common eating method is all often that gross weight band meat is eaten together after simply cleaning, and dives
Residues of pesticides certain harm to the health of eater be present, it is therefore necessary to qualitative, quantitative is done to the residues of pesticides in blueberry
Monitoring.The national standard method that China is not measured specifically for blueberry Pesticide Residues at present, typically joins
According to《The measure GB/T5009.218-2008 of Multi-pesticide residues in fruits and vegetables》Or《National food safety standard water
500 kinds of agricultural chemicals and the measure gas chromatography-mass spectrography GB23200.8-2016 of related chemicals residual quantity in fruit and vegetables》And
《The measure gas chromatography-mass spectrography NY/T 1380-2007 of 51 kinds of pesticide multi-residues in veterinary antibiotics》, these normative references one
Aspect is required for using the very high organic reagent of a large amount of purity, and these reagents inevitably produce health to experimenter
Harm, on the other hand also needs to use expensive various solid phase adsorption pillars, these reagents and pillar after use again
Have to obtain appropriate processing, it is generally time-consuming, laborious and with high costs, so quick, economic, efficient, ring must be developed
Protect and the accurate method of science carries out qualitative and quantitative detection to the residues of pesticides in blueberry.
The content of the invention
For the deficiencies in the prior art, the technical problems to be solved by the invention be to provide it is a kind of simple, quick,
The method for determining remains of pesticide in blueberry exactly.
The technical problems to be solved by the invention, it is achieved by the following technical solution：
Quick determination method in a kind of blueberry in Multiple Pesticides residual blueberry, it is characterised in that be made up of following step：
(1) blueberry is homogenized with refiner, adds water and acetonitrile is disperseed；
(2) magnetic metal-organic framework materials (MOFs) are put into be extracted；
(3) magnetic metal-organic framework materials for being adsorbed with agricultural chemicals are separated from blueberry solution using magnet；
(4) agricultural chemicals adsorbed in magnetic metal-organic framework materials is eluted using organic solvent；
(5) analysis detection is carried out to elution solution using gas chromatograph/mass spectrometer.
The fast method that Multiple Pesticides detect simultaneously in a kind of blueberry, is made up of following step：
(1) blueberry is homogenized with refiner, obtains blueberry pulp；4.5-5.5g blueberry pulps are taken to be filled in tool in centrifuge tube,
8-12mL water, 0.8-1.2mL acetonitriles are added, is well mixed, obtains mixed liquor；
(2) 30-50mg magnetic metals-organic framework materials are added to fill in centrifuge tube in tool, extract 3-5min；
(3) magnet is put in tool plug centrifuge tube side wall, is adsorbed with magnetic metal-organic framework materials of agricultural chemicals because possessing
Magnetic, therefore be attracted in the side wall close to magnet, discards mixed liquor, with water to being adsorbed with the magnetic metal of agricultural chemicals-organic
Frame material is cleaned, and discards cleaning fluid；
(4) ultrasonic elution is carried out to magnetic metal-organic framework materials using 1-3mL organic solvents, obtains eluent；So
Eluent is concentrated into 0.9-1.1mL on nitrogen evaporator afterwards, obtains concentrate；
(5) quantitative internal standard is added in concentrate, is analyzed with GC/MS instruments, is carried out using internal mark working curve method
Qualitative, quantitative determines, by the result that blueberry Pesticide Residues are calculated.
Preferably, the capacity of the tool plug centrifuge tube is 20-30mL.
Preferably, the method for extraction is extracted for concussion in the step (2).
Preferably, the magnetic metal-organic framework materials are ferroso-ferric oxide@silica@Dopamine hydrochlorides.
The preparation method of the ferroso-ferric oxide@silica@Dopamine hydrochlorides is：Take 1-1.5g FeCl3·6H2O adds
Enter in 70-80mL ethylene glycol and stir 20-40min, continue to stir 50-70min after adding 3.2-3.8g sodium acetates, mixed
Material；Compound is transferred in the autoclave for the teflon lined stainless steel that capacity is 150-250mL, in 180-
10-14h is heated at 220 DEG C, obtains black particles；Black particles are collected by externally-applied magnetic field, and is cleaned and done with ethanol
Only, 5-15h is dried in vacuo at 45-55 DEG C, obtains Fe3O4Magnetic core；Take 45-55mgFe3O4Magnetic core and 450-550mg quaternary ammonium salts
Add in 45-55mL water, carry out supersound process 2-10min, obtain dispersion liquid；400-500mL hydroxides are added in dispersion liquid
The molar concentration of sodium hydroxide is 0.2-1.2mol/L in sodium water solution, wherein sodium hydrate aqueous solution, continues to be ultrasonically treated 3-
7min, then the heating stirring 25-35min in 55-65 DEG C of oil bath；Then by 2-3mL tetraethyl orthosilicates/ethanol solution dropwise
Add, tetraethyl orthosilicate, the volume ratio of ethanol are 1 wherein in tetraethyl orthosilicate/ethanol solution：(3-5), continues at 55-65 DEG C
Heating stirring 25-35min in oil bath；Then 280-320mg dopamine hydrochlorides, 180-220mL trihydroxy methyl amino first are added
The alkane aqueous solution, the molar concentration of trishydroxymethylaminomethane is 0.5-1.2mol/ in the trishydroxymethylaminomethane aqueous solution
L, continue the heating stirring 10-14h in 55-65 DEG C of oil bath, collected in the presence of externally-applied magnetic field, cleaned with water, then use acetone
Cleaning, is finally dried in vacuo 5-15h at 45-55 DEG C, obtains ferroso-ferric oxide@silica@Dopamine hydrochlorides (Fe3O4@m-
SiO2/PSA).Mesoporous SiO2 shells are coated on Fe3O4Mainly there are two functions on magnetic core surface：(I)SiO2The presence of shell is favourable
In the modification that organic molecule is next carried out on magnetic microsphere surface；(II)SiO2The protection internal layer Fe of shell3O4Magnetic core is in reality
It is not destroyed in.
It is further preferred that magnetic metal-the organic framework materials are ferroso-ferric oxide@silica@hydrochloric acid DOPA
Amine@zirconiums.
The preparation method of the ferroso-ferric oxide@silica@Dopamine hydrochloride@zirconiums is：Take 1-1.5g FeCl3·6H2O
Add in 70-80mL ethylene glycol and stir 20-40min, continue to stir 50-70min after adding 3.2-3.8g sodium acetates, mixed
Close material；Compound is transferred in the autoclave for the teflon lined stainless steel that capacity is 150-250mL,
10-14h is heated at 180-220 DEG C, obtains black particles；Black particles are collected by externally-applied magnetic field, and it is clear with ethanol
Wash clean, 5-15h is dried in vacuo at 45-55 DEG C, obtains Fe3O4Magnetic core；Take 45-55mgFe3O4Magnetic core and 450-550mg seasons
Ammonium salt is added in 45-55mL water, is carried out supersound process 2-10min, is obtained dispersion liquid；400-500mL hydrogen is added in dispersion liquid
The molar concentration of sodium hydroxide is 0.2-1.2mol/L in aqueous solution of sodium oxide, wherein sodium hydrate aqueous solution, is continued at ultrasound
3-7min is managed, then the heating stirring 25-35min in 55-65 DEG C of oil bath；Then by 2-3mL tetraethyl orthosilicates/ethanol solution
It is added dropwise, tetraethyl orthosilicate, the volume ratio of ethanol are 1 wherein in tetraethyl orthosilicate/ethanol solution：(3-5), continues in 55-
Heating stirring 25-35min in 65 DEG C of oil baths；Then 280-320mg dopamine hydrochlorides, 180-220mL trihydroxy methyl ammonia are added
The methylmethane aqueous solution, the molar concentration of trishydroxymethylaminomethane is 0.5- in the trishydroxymethylaminomethane aqueous solution
1.2mol/L, continue the heating stirring 10-14h in 55-65 DEG C of oil bath, collected in the presence of externally-applied magnetic field, cleaned with water, then
Cleaned with acetone, be finally dried in vacuo 5-15h at 45-55 DEG C, obtain ferroso-ferric oxide@silica@Dopamine hydrochlorides
(Fe3O4@m-SiO2/PSA)；90-110mg ferroso-ferric oxide@silica@Dopamine hydrochlorides are taken to add 35-45mL N, N- bis-
In NMF, 75-80mg ZrCl are added4With 8-12mg terephthalic acid (TPA)s, 15- is heated under the conditions of 130-150 DEG C
25min, collect in the presence of externally-applied magnetic field, then cleaned successively with water and methanol, be dried in vacuo 5-15h at 45-55 DEG C, obtain
To ferroso-ferric oxide@silica@Dopamine hydrochloride@zirconiums (Fe3O4@m-SiO2/PSA@Zr-MOF)。
The quaternary ammonium salt is cetyl trimethylammonium bromide and/or lauryl trimethyl ammonium bromide.Of the invention one
In embodiment, the quaternary ammonium salt is by 85-95wt% cetyl trimethylammonium bromides and 5-15wt% lauryl trimethyl bromines
Change ammonium composition.
Preferably, the number of cleaning is 2-3 times in the step (3), and the dosage of each rinse water is 1-3mL.
Preferably, the organic solvent is (2-4) by volume by acetonitrile, methanol：1 mixes.
Preferably, the quantitative interior acetonitrile solution for being designated as 2,4,6- tri- bromo biphenyls, wherein 2,4,6- tri- bromo biphenyls is dense
Spend for 0.9-1.1mg/mL；The quantitative interior target addition is 8-12 μ L.
Relative to prior art, the advantage of the invention is that：The Multiple Pesticides in Blueberry are remained using this method
Progress determines simultaneously, and method is quick, economical, efficiently and accurate, substantially reduces minute and cost, reduces to personnel and environment
Harmful effect.
Embodiment
By embodiment, the invention will be further described, but the present invention is not limited by following examples.
Blueberry in embodiment
Acetonitrile in embodiment, No. CAS：75-05-8.
Methanol in embodiment, No. CAS：67-56-1.
2,4,6- tri- bromo biphenyl in embodiment, No. CAS：59080-33-0.
FeCl in embodiment3·6H2O, No. CAS：10025-77-1.
Ethylene glycol in embodiment, No. CAS：107-21-1.
Sodium acetate in embodiment, No. CAS：127-09-3.
Ethanol in embodiment, No. CAS：64-17-5.
Cetyl trimethylammonium bromide in embodiment, No. CAS：57-09-0.
Lauryl trimethyl ammonium bromide in embodiment, No. CAS：1119-94-4.
Sodium hydroxide in embodiment, No. CAS：1310-73-2.
Tetraethyl orthosilicate in embodiment, No. CAS：78-10-4.
Dopamine hydrochloride in embodiment, No. CAS：62-31-7.
Trishydroxymethylaminomethane in embodiment, No. CAS：77-86-1.
Acetone in embodiment, No. CAS：67-64-1.
DMF in embodiment, No. CAS：68-12-2.
ZrCl in embodiment4, No. CAS：10026-11-6.
Terephthalic acid (TPA) in embodiment, No. CAS：100-21-0.
Refiner is the inscribe for the model XHF-DY that NingBo XinZhi Biology Science Co., Ltd provides in embodiment
Formula refiner (also known as high speed disperser).
Eddy mixer is the whirlpool for the model MIN-28+ that Changzhou En Pei instrument manufacturings Co., Ltd provides in embodiment
Blender.
The agricultural chemicals and chromatographic mass spectrometry information detected is shown in Table 1.
Table 1：The title of 15 kinds of agricultural chemicals, retention time, qualitative, quantitative ion statistical form
Embodiment 1
(1) 100.0g blueberries are subjected to homogenate 5min with refiner using rotating speed as 8000 revs/min, obtain blueberry pulp；Take
5.0g blueberry pulps have in plug centrifuge tube in 25mL, add 10mL deionized waters, 1mL acetonitriles, with eddy mixer using rotating speed as
2500 revs/min of concussion 2min are well mixed, and obtain mixed liquor；
(2) 40mg magnetic metals-organic framework materials are added in the 25mL tool plug centrifuge tubes of step (1), use whirlpool
Blender is using rotating speed as 2500 revs/min of concussion extraction 4min；
(3) have plug centrifuge tube side wall in 25mL and put magnet, it is to be adsorbed have agricultural chemicals magnetic metal-organic framework materials it is complete
It is complete to be attracted in the side wall of magnet, mixed liquor is discarded, magnetic metal-organic framework materials are carried out clearly with deionized water
Wash 3 times, the dosage for cleaning deionized water every time is 2mL, discards cleaning fluid.
(4) acetonitrile/methanol volume ratio is used as 3:1 organic solvent 2mL has magnetic metal-have in plug centrifuge tube to 25mL
Machine frame frame material carries out ultrasound elution 5min, wherein the ultrasonic power of ultrasound elution is 150W, supersonic frequency 40KHz,
The agricultural chemicals adsorbed is eluted to acetonitrile/methanol volume ratio as 3 from magnetic metal-organic framework materials:In 1 organic solvent, obtain
To eluent；Then eluent is concentrated into 1mL on nitrogen evaporator, obtains concentrate.
(5) quantitative internal standard is added in concentrate, it is described to quantify the interior acetonitrile solution for being designated as 2,4,6- tri- bromo biphenyls, wherein
The concentration of the bromo biphenyls of 2,4,6- tri- is 1mg/mL；The quantitative interior target addition is 10 μ L；Analyzed with GC/MS instruments,
Qualitative, quantitative measure is carried out using internal mark working curve method, by the result that blueberry Pesticide Residues are calculated.
Magnetic metal-the organic framework materials are ferroso-ferric oxide@silica@Dopamine hydrochlorides.
The preparation method of the ferroso-ferric oxide@silica@Dopamine hydrochlorides is：Take 1.35g FeCl3·6H2O is added
30min is stirred by 150r/min of rotating speed in 75mL ethylene glycol, is continued after adding 3.6g sodium acetates using rotating speed as 150r/min
60min is stirred, obtains compound；Compound is transferred to the high pressure for the teflon lined stainless steel that capacity is 200mL
In reactor, 12h is heated at 200 DEG C, obtains black particles；Black particles are collected by externally-applied magnetic field, and use 3mL
Ethanol cleans up, and is dried in vacuo 10h in the case where temperature is 50 DEG C, vacuum is 130Pa, obtains Fe3O4Magnetic core；Take 50mg
Fe3O4Magnetic core and 500mg cetyl trimethylammonium bromides are added in 50mL deionized waters, carry out supersound process 5min, wherein super
The ultrasonic power of sonication is 150W, supersonic frequency 40KHz, obtains dispersion liquid；450mL hydroxides are added in dispersion liquid
The molar concentration of sodium hydroxide is 0.6mol/L in sodium water solution, wherein sodium hydrate aqueous solution, continues to be ultrasonically treated 5min, so
Afterwards 30min is stirred in 50 DEG C of oil bath by 150r/min of rotating speed；Then by 2.5mL tetraethyl orthosilicates/ethanol solution dropwise
Add, tetraethyl orthosilicate, the volume ratio of ethanol are 1 in rate of addition 0.05mL/s, wherein tetraethyl orthosilicate/ethanol solution：
4, continue to stir 30min by 150r/min of rotating speed in 60 DEG C of oil baths；Then 300mg dopamine hydrochlorides, 200mL tri- are added
The hydroxymethyl aminomethane aqueous solution, the molar concentration of trishydroxymethylaminomethane is in the trishydroxymethylaminomethane aqueous solution
1mol/L, continue to stir 12h by 150r/min of rotating speed in 60 DEG C of oil baths, collect in the presence of externally-applied magnetic field, gone with 3mL
Ionized water cleans, then is cleaned with 3mL acetone, is finally dried in vacuo 10h in the case where temperature is 50 DEG C, vacuum is 130Pa, obtains four
Fe 3 O@silica@Dopamine hydrochlorides (Fe3O4@m-SiO2/PSA).Mesoporous SiO2 shells are coated on Fe3O4Magnetic core surface
Mainly there are two functions：(I)SiO2The presence of shell has beneficial to the modification that organic molecule is next carried out on magnetic microsphere surface；
(II)SiO2The protection internal layer Fe of shell3O4Magnetic core is not destroyed in actual applications.
Analyze the instrument used and condition is as follows：
Using Agilent 7890B/5977 gas chromatography-mass spectrometries：
Chromatographic column：DB-5ms quartz capillary chromatographic columns (30m × 0.25mm × 0.25 μm, Agilent)
Column temperature：40 DEG C of holding 1min, then with 30 DEG C/min temperature programmings to 130 DEG C, then with 5 DEG C/min are warming up to 250
DEG C, then 300 DEG C are warming up to 10 DEG C/min, keep 8min；
Carrier gas：Helium, purity >=99.999%, flow velocity：1.2mL/min；
Injector temperature：280℃
Ion source temperature：230℃
Quadrupole rod temperature：150℃
Carrier gas (flow)：He (1.0mL/min,>99.999%)
Sample size：1.0μL
Input mode：Splitless injecting samples.
Mass detector：EI sources, 70eV.
Salbutamol Selected Ion Monitoring：Every kind of compound selects a quota ion, the choosing of 2~3 qualitative ions, wherein internal standard respectively
2,4,6- tri- bromo biphenyls, detection ion are 248,250,390,392.
The indices of the method for embodiment 1 are shown in Table 2.
Table 2：15 kinds of agricultural chemicals test result statistical forms of embodiment 1
Embodiment 2
(1) 100.0g blueberries are subjected to homogenate 5min with refiner using rotating speed as 8000 revs/min, obtain blueberry pulp；Take
5.0g blueberry pulps have in plug centrifuge tube in 25mL, add 10mL deionized waters, 1mL acetonitriles, with eddy mixer using rotating speed as
2500 revs/min of concussion 2min are well mixed, and obtain mixed liquor；
(2) 40mg magnetic metals-organic framework materials are added in the 25mL tool plug centrifuge tubes of step (1), use whirlpool
Blender is using rotating speed as 2500 revs/min of concussion extraction 4min；
(3) have plug centrifuge tube side wall in 25mL and put magnet, it is to be adsorbed have agricultural chemicals magnetic metal-organic framework materials it is complete
It is complete to be attracted in the side wall of magnet, mixed liquor is discarded, magnetic metal-organic framework materials are carried out clearly with deionized water
Wash 3 times, the dosage for cleaning deionized water every time is 2mL, discards cleaning fluid.
(4) acetonitrile/methanol volume ratio is used as 3:1 organic solvent 2mL has magnetic metal-have in plug centrifuge tube to 25mL
Machine frame frame material carries out ultrasound elution 5min, wherein the ultrasonic power of ultrasound elution is 150W, supersonic frequency 40KHz,
The agricultural chemicals adsorbed is eluted to acetonitrile/methanol volume ratio as 3 from magnetic metal-organic framework materials:In 1 organic solvent, obtain
To eluent；Then eluent is concentrated into 1mL on nitrogen evaporator, obtains concentrate.
(5) quantitative internal standard is added in concentrate, it is described to quantify the interior acetonitrile solution for being designated as 2,4,6- tri- bromo biphenyls, wherein
The concentration of the bromo biphenyls of 2,4,6- tri- is 1mg/mL；The quantitative interior target addition is 10 μ L；Analyzed with GC/MS instruments,
Qualitative, quantitative measure is carried out using internal mark working curve method, by the result that blueberry Pesticide Residues are calculated.
Magnetic metal-the organic framework materials are ferroso-ferric oxide@silica@Dopamine hydrochloride@zirconiums.
The preparation method of the ferroso-ferric oxide@silica@Dopamine hydrochloride@zirconiums is：Take 1.35gFeCl3·6H2O adds
Enter in 75mL ethylene glycol and stir 30min by 150r/min of rotating speed, continue after adding 3.6g sodium acetates using rotating speed as 150r/
Min stirs 60min, obtains compound；Compound is transferred to the height for the teflon lined stainless steel that capacity is 200mL
Press in reactor, heat 12h at 200 DEG C, obtain black particles；Black particles are collected by externally-applied magnetic field, are used in combination
3mL ethanol cleans up, and is dried in vacuo 10h in the case where temperature is 50 DEG C, vacuum is 130Pa, obtains Fe3O4Magnetic core；Take 50mg
Fe3O4Magnetic core and 500mg cetyl trimethylammonium bromides are added in 50mL deionized waters, carry out supersound process 5min, wherein super
The ultrasonic power of sonication is 150W, supersonic frequency 40KHz, obtains dispersion liquid；450mL hydroxides are added in dispersion liquid
The molar concentration of sodium hydroxide is 0.6mol/L in sodium water solution, wherein sodium hydrate aqueous solution, continues to be ultrasonically treated 5min, so
Afterwards 30min is stirred in 50 DEG C of oil bath by 150r/min of rotating speed；Then by 2.5mL tetraethyl orthosilicates/ethanol solution dropwise
Add, tetraethyl orthosilicate, the volume ratio of ethanol are 1 in rate of addition 0.05mL/s, wherein tetraethyl orthosilicate/ethanol solution：
4, continue to stir 30min by 150r/min of rotating speed in 60 DEG C of oil baths；Then 300mg dopamine hydrochlorides, 200mL tri- are added
The hydroxymethyl aminomethane aqueous solution, the molar concentration of trishydroxymethylaminomethane is in the trishydroxymethylaminomethane aqueous solution
1mol/L, continue to stir 12h by 150r/min of rotating speed in 60 DEG C of oil baths, collect in the presence of externally-applied magnetic field, gone with 3mL
Ionized water cleans, then is cleaned with 3mL acetone, is finally dried in vacuo 10h in the case where temperature is 50 DEG C, vacuum is 130Pa, obtains four
Fe 3 O@silica@Dopamine hydrochlorides (Fe3O4@m-SiO2/PSA)；Take 100mg ferroso-ferric oxide@silica@hydrochloric acid
Dopamine adds 40mLN, in dinethylformamide, adds 78mg ZrCl4With 10mg terephthalic acid (TPA)s, under the conditions of 140 DEG C
20min is heated, is collected in the presence of externally-applied magnetic field, then is cleaned successively with 3mL deionized waters and 3mL methanol, is 50 in temperature
DEG C, vacuum be 130Pa under be dried in vacuo 10h, obtain ferroso-ferric oxide@silica@Dopamine hydrochloride@zirconiums (Fe3O4@m-
SiO2/PSA@Zr-MOF)。
The indices of the method for embodiment 2 are shown in Table 3.
Table 3：15 kinds of agricultural chemicals test result statistical forms of embodiment 2
Embodiment 3
(1) 100.0g blueberries are subjected to homogenate 5min with refiner using rotating speed as 8000 revs/min, obtain blueberry pulp；Take
5.0g blueberry pulps have in plug centrifuge tube in 25mL, add 10mL deionized waters, 1mL acetonitriles, with eddy mixer using rotating speed as
2500 revs/min of concussion 2min are well mixed, and obtain mixed liquor；
(2) 40mg magnetic metals-organic framework materials are added in the 25mL tool plug centrifuge tubes of step (1), use whirlpool
Blender is using rotating speed as 2500 revs/min of concussion extraction 4min；
(3) have plug centrifuge tube side wall in 25mL and put magnet, it is to be adsorbed have agricultural chemicals magnetic metal-organic framework materials it is complete
It is complete to be attracted in the side wall of magnet, mixed liquor is discarded, magnetic metal-organic framework materials are carried out clearly with deionized water
Wash 3 times, the dosage for cleaning deionized water every time is 2mL, discards cleaning fluid.
(4) acetonitrile/methanol volume ratio is used as 3:1 organic solvent 2mL has magnetic metal-have in plug centrifuge tube to 25mL
Machine frame frame material carries out ultrasound elution 5min, wherein the ultrasonic power of ultrasound elution is 150W, supersonic frequency 40KHz,
The agricultural chemicals adsorbed is eluted to acetonitrile/methanol volume ratio as 3 from magnetic metal-organic framework materials:In 1 organic solvent, obtain
To eluent；Then eluent is concentrated into 1mL on nitrogen evaporator, obtains concentrate.
(5) quantitative internal standard is added in concentrate, it is described to quantify the interior acetonitrile solution for being designated as 2,4,6- tri- bromo biphenyls, wherein
The concentration of the bromo biphenyls of 2,4,6- tri- is 1mg/mL；The quantitative interior target addition is 10 μ L；Analyzed with GC/MS instruments,
Qualitative, quantitative measure is carried out using internal mark working curve method, by the result that blueberry Pesticide Residues are calculated.
Magnetic metal-the organic framework materials are ferroso-ferric oxide@silica@Dopamine hydrochloride@zirconiums.
The preparation method of the ferroso-ferric oxide@silica@Dopamine hydrochloride@zirconiums is：Take 1.35g FeCl3·6H2O
Add in 75mL ethylene glycol and stir 30min by 150r/min of rotating speed, continue after adding 3.6g sodium acetates using rotating speed as 150r/
Min stirs 60min, obtains compound；Compound is transferred to the height for the teflon lined stainless steel that capacity is 200mL
Press in reactor, heat 12h at 200 DEG C, obtain black particles；Black particles are collected by externally-applied magnetic field, are used in combination
3mL ethanol cleans up, and is dried in vacuo 10h in the case where temperature is 50 DEG C, vacuum is 130Pa, obtains Fe3O4Magnetic core；Take 50mg
Fe3O4Magnetic core and 500mg lauryl trimethyls ammonium bromide are added in 50mL deionized waters, carry out supersound process 5min, wherein ultrasound
The ultrasonic power of processing is 150W, supersonic frequency 40KHz, obtains dispersion liquid；450mL sodium hydroxides are added in dispersion liquid
The molar concentration of sodium hydroxide is 0.6mol/L in the aqueous solution, wherein sodium hydrate aqueous solution, continues to be ultrasonically treated 5min, then
In 50 DEG C of oil bath 30min is stirred by 150r/min of rotating speed；Then 2.5mL tetraethyl orthosilicates/ethanol solution is added dropwise
Enter, rate of addition 0.05mL/s, tetraethyl orthosilicate, the volume ratio of ethanol are 1 wherein in tetraethyl orthosilicate/ethanol solution：4,
Continue to stir 30min by 150r/min of rotating speed in 60 DEG C of oil baths；Then 300mg dopamine hydrochlorides, the hydroxyls of 200mL tri- are added
The aminomethane aqueous solution, the molar concentration of trishydroxymethylaminomethane is in the trishydroxymethylaminomethane aqueous solution
1mol/L, continue to stir 12h by 150r/min of rotating speed in 60 DEG C of oil baths, collect in the presence of externally-applied magnetic field, gone with 3mL
Ionized water cleans, then is cleaned with 3mL acetone, is finally dried in vacuo 10h in the case where temperature is 50 DEG C, vacuum is 130Pa, obtains four
Fe 3 O@silica@Dopamine hydrochlorides (Fe3O4@m-SiO2/PSA)；Take 100mg ferroso-ferric oxide@silica@hydrochloric acid
Dopamine adds 40mLN, in dinethylformamide, adds 78mg ZrCl4With 10mg terephthalic acid (TPA)s, under the conditions of 140 DEG C
20min is heated, is collected in the presence of externally-applied magnetic field, then is cleaned successively with 3mL deionized waters and 3mL methanol, is 50 in temperature
DEG C, vacuum be 130Pa under be dried in vacuo 10h, obtain ferroso-ferric oxide@silica@Dopamine hydrochloride@zirconiums (Fe3O4@m-
SiO2/PSA@Zr-MOF)。
The indices of the method for embodiment 3 are shown in Table 4.
Table 4：15 kinds of agricultural chemicals test result statistical forms of embodiment 3
Embodiment 4
(1) 100.0g blueberries are subjected to homogenate 5min with refiner using rotating speed as 8000 revs/min, obtain blueberry pulp；Take
5.0g blueberry pulps have in plug centrifuge tube in 25mL, add 10mL deionized waters, 1mL acetonitriles, with eddy mixer using rotating speed as
2500 revs/min of concussion 2min are well mixed, and obtain mixed liquor；
(2) 40mg magnetic metals-organic framework materials are added in the 25mL tool plug centrifuge tubes of step (1), use whirlpool
Blender is using rotating speed as 2500 revs/min of concussion extraction 4min；
(3) have plug centrifuge tube side wall in 25mL and put magnet, it is to be adsorbed have agricultural chemicals magnetic metal-organic framework materials it is complete
It is complete to be attracted in the side wall of magnet, mixed liquor is discarded, magnetic metal-organic framework materials are carried out clearly with deionized water
Wash 3 times, the dosage for cleaning deionized water every time is 2mL, discards cleaning fluid.
(4) acetonitrile/methanol volume ratio is used as 3:1 organic solvent 2mL has magnetic metal-have in plug centrifuge tube to 25mL
Machine frame frame material carries out ultrasound elution 5min, wherein the ultrasonic power of ultrasound elution is 150W, supersonic frequency 40KHz,
The agricultural chemicals adsorbed is eluted to acetonitrile/methanol volume ratio as 3 from magnetic metal-organic framework materials:In 1 organic solvent, obtain
To eluent；Then eluent is concentrated into 1mL on nitrogen evaporator, obtains concentrate.
(5) quantitative internal standard is added in concentrate, it is described to quantify the interior acetonitrile solution for being designated as 2,4,6- tri- bromo biphenyls, wherein
The concentration of the bromo biphenyls of 2,4,6- tri- is 1mg/mL；The quantitative interior target addition is 10 μ L；Analyzed with GC/MS instruments,
Qualitative, quantitative measure is carried out using internal mark working curve method, by the result that blueberry Pesticide Residues are calculated.
Magnetic metal-the organic framework materials are ferroso-ferric oxide@silica@Dopamine hydrochloride@zirconiums.
The preparation method of the ferroso-ferric oxide@silica@Dopamine hydrochloride@zirconiums is：Take 1.35gFeCl3·6H2O adds
Enter in 75mL ethylene glycol and stir 30min by 150r/min of rotating speed, continue after adding 3.6g sodium acetates using rotating speed as 150r/
Min stirs 60min, obtains compound；Compound is transferred to the height for the teflon lined stainless steel that capacity is 200mL
Press in reactor, heat 12h at 200 DEG C, obtain black particles；Black particles are collected by externally-applied magnetic field, are used in combination
3mL ethanol cleans up, and is dried in vacuo 10h in the case where temperature is 50 DEG C, vacuum is 130Pa, obtains Fe3O4Magnetic core；Take 50mg
Fe3O4Magnetic core, 450mg cetyl trimethylammonium bromides and 50mg lauryl trimethyls ammonium bromide are added in 50mL deionized waters,
Supersound process 5min is carried out, wherein the ultrasonic power being ultrasonically treated is 150W, supersonic frequency 40KHz, obtains dispersion liquid；
450mL sodium hydrate aqueous solutions are added in dispersion liquid, wherein the molar concentration of sodium hydroxide is in sodium hydrate aqueous solution
0.6mol/L, continue to be ultrasonically treated 5min, then stir 30min by 150r/min of rotating speed in 50 DEG C of oil bath；Then will
2.5mL tetraethyl orthosilicates/ethanol solution is added dropwise, rate of addition 0.05mL/s, wherein in tetraethyl orthosilicate/ethanol solution
Tetraethyl orthosilicate, the volume ratio of ethanol are 1：4, continue to stir 30min by 150r/min of rotating speed in 60 DEG C of oil baths；Then plus
Enter 300mg dopamine hydrochlorides, the 200mL trishydroxymethylaminomethane aqueous solution, in the trishydroxymethylaminomethane aqueous solution
The molar concentration of trishydroxymethylaminomethane is 1mol/L, continues to stir 12h by 150r/min of rotating speed in 60 DEG C of oil baths,
Collect in the presence of externally-applied magnetic field, cleaned with 3mL deionized waters, then cleaned with 3mL acetone, be finally 50 DEG C, vacuum in temperature
Spend to be dried in vacuo 10h under 130Pa, obtain ferroso-ferric oxide@silica@Dopamine hydrochlorides (Fe3O4@m-SiO2/PSA)；Take
100mg ferroso-ferric oxide@silica@Dopamine hydrochlorides add 40mLN, in dinethylformamide, add 78mg ZrCl4
With 10mg terephthalic acid (TPA)s, 20min is heated under the conditions of 140 DEG C, is collected in the presence of externally-applied magnetic field, then is gone successively with 3mL
Ionized water and the cleaning of 3mL methanol, are dried in vacuo 10h in the case where temperature is 50 DEG C, vacuum is 130Pa, obtain ferroso-ferric oxide@bis-
Silica@Dopamine hydrochloride@zirconiums (Fe3O4@m-SiO2/PSA@Zr-MOF)。
Analyze the instrument used and condition is as follows：
Using Agilent 7890B/5977 gas chromatography-mass spectrometries：
Chromatographic column：DB-5ms quartz capillary chromatographic columns (30m × 0.25mm × 0.25 μm, Agilent)
Column temperature：40 DEG C of holding 1min, then with 30 DEG C/min temperature programmings to 130 DEG C, then with 5 DEG C/min are warming up to 250
DEG C, then 300 DEG C are warming up to 10 DEG C/min, keep 8min；
Carrier gas：Helium, purity >=99.999%, flow velocity：1.2mL/min；
Injector temperature：280℃
Ion source temperature：230℃
Quadrupole rod temperature：150℃
Carrier gas (flow)：He (1.0mL/min,>99.999%)
Sample size：1.0μL
Input mode：Splitless injecting samples.
Mass detector：EI sources, 70eV.
Salbutamol Selected Ion Monitoring：Every kind of compound selects a quota ion, the choosing of 2~3 qualitative ions, wherein internal standard respectively
2,4,6- tri- bromo biphenyls, detection ion are 248,250,390,392.
The indices of the method for embodiment 4 are shown in Table 5.
Table 5：15 kinds of agricultural chemicals test result statistical forms of embodiment 4
The foregoing is only a specific embodiment of the invention, 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 change that creative work is expected or
Replace, should all be included within the scope of the present invention.Therefore, protection scope of the present invention should be limited with claims
Fixed protection domain is defined.
Claims (10)
1. the quick determination method that Multiple Pesticides remain in a kind of blueberry, it is characterised in that be made up of following step：
(1) blueberry is homogenized with refiner, adds water and acetonitrile is disperseed；
(2) input magnetic metal-organic framework materials are extracted；
(3) magnetic metal-organic framework materials for being adsorbed with agricultural chemicals are separated from blueberry solution using magnet；
(4) agricultural chemicals adsorbed in magnetic metal-organic framework materials is eluted using organic solvent；
(5) analysis detection is carried out to elution solution using gas chromatograph/mass spectrometer.
2. the quick determination method that Multiple Pesticides remain in blueberry as claimed in claim 1, it is characterised in that by following step
Composition：
(1) blueberry is homogenized with refiner, obtains blueberry pulp；Take 4.5-5.5g blueberry pulps to be filled in tool in centrifuge tube, add
8-12mL water, 0.8-1.2mL acetonitriles, it is well mixed, obtains mixed liquor；
(2) 30-50mg magnetic metals-organic framework materials are added to fill in centrifuge tube in tool, extract 3-5min；
(3) magnet is put in tool plug centrifuge tube side wall, is adsorbed with magnetic metal-organic framework materials of agricultural chemicals because possessing magnetic
Property, therefore it is attracted in the side wall close to magnet, discards mixed liquor, with water to being adsorbed with the magnetic metal of agricultural chemicals-have machine frame
Frame material is cleaned, and discards cleaning fluid；
(4) ultrasonic elution is carried out to magnetic metal-organic framework materials using 1-3mL organic solvents, obtains eluent；Then exist
Eluent is concentrated into 0.9-1.1mL on nitrogen evaporator, obtains concentrate；
(5) quantitative internal standard is added in concentrate, is analyzed with GC/MS instruments, is carried out using internal mark working curve method qualitative
Quantitative determination, by the result that blueberry Pesticide Residues are calculated.
3. the quick determination method that Multiple Pesticides remain in blueberry as claimed in claim 1 or 2, it is characterised in that：The step
Suddenly the method for extraction is extracted for concussion in (2).
4. the quick determination method that Multiple Pesticides remain in blueberry as claimed in claim 1 or 2, it is characterised in that：It is described to have
Solvent is (2-4) by volume by acetonitrile, methanol：1 mixes.
5. the quick determination method that Multiple Pesticides remain in blueberry as claimed in claim 1 or 2, it is characterised in that：The magnetic
Property metal-organic framework materials are ferroso-ferric oxide@silica@Dopamine hydrochlorides；The ferroso-ferric oxide@silica@
The preparation method of Dopamine hydrochloride is：Take 1-1.5g FeCl3·6H2O is added in 70-80mL ethylene glycol and is stirred 20-40min, then
Continue to stir 50-70min after adding 3.2-3.8g sodium acetates, obtain compound；It is 150-250mL's that compound is transferred into capacity
In the autoclave of teflon lined stainless steel, 10-14h is heated at 180-220 DEG C, obtains black particles；
Black particles are collected by externally-applied magnetic field, and cleaned up with ethanol, 5-15h is dried in vacuo at 45-55 DEG C, obtains
Fe3O4Magnetic core；Take 45-55mgFe3O4Magnetic core and 450-550mg quaternary ammonium salts are added in 45-55mL water, carry out supersound process 2-
10min, obtain dispersion liquid；400-500mL sodium hydrate aqueous solutions, wherein hydrogen in sodium hydrate aqueous solution are added in dispersion liquid
The molar concentration of sodium oxide molybdena is 0.2-1.2mol/L, continues to be ultrasonically treated 3-7min, then heats and stir in 55-65 DEG C of oil bath
Mix 25-35min；Then 2-3mL tetraethyl orthosilicates/ethanol solution is added dropwise, wherein in tetraethyl orthosilicate/ethanol solution just
Silester, the volume ratio of ethanol are 1：(3-5), continue the heating stirring 25-35min in 55-65 DEG C of oil bath；Then add
280-320mg dopamine hydrochlorides, the 180-220mL trishydroxymethylaminomethane aqueous solution, the trishydroxymethylaminomethane water
The molar concentration of trishydroxymethylaminomethane is 0.5-1.2mol/L in solution, continues the heating stirring 10- in 55-65 DEG C of oil bath
14h, collect in the presence of externally-applied magnetic field, cleaned with water, then cleaned with acetone, be finally dried in vacuo 5- at 45-55 DEG C
15h, obtain ferroso-ferric oxide@silica@Dopamine hydrochlorides.
6. the quick determination method that Multiple Pesticides remain in blueberry as claimed in claim 1 or 2, it is characterised in that：The magnetic
Property metal-organic framework materials are ferroso-ferric oxide@silica@Dopamine hydrochloride@zirconiums；The ferroso-ferric oxide@titanium dioxides
The preparation method of silicon@Dopamine hydrochloride@zirconiums is：Take 1-1.5g FeCl3·6H2O is added in 70-80mL ethylene glycol and is stirred 20-
40min, continue to stir 50-70min after adding 3.2-3.8g sodium acetates, obtain compound；Compound is transferred into capacity is
In the autoclave of 150-250mL teflon lined stainless steel, 10-14h is heated at 180-220 DEG C, is obtained
To black particles；Black particles are collected by externally-applied magnetic field, and cleaned up with ethanol, vacuum is done at 45-55 DEG C
Dry 5-15h, obtains Fe3O4Magnetic core；Take 45-55mgFe3O4Magnetic core and 450-550mg quaternary ammonium salts are added in 45-55mL water, are carried out
2-10min is ultrasonically treated, obtains dispersion liquid；400-500mL sodium hydrate aqueous solutions, wherein sodium hydroxide are added in dispersion liquid
The molar concentration of sodium hydroxide is 0.2-1.2mol/L in the aqueous solution, continues to be ultrasonically treated 3-7min, then in 55-65 DEG C of oil
Heating stirring 25-35min in bath；Then 2-3mL tetraethyl orthosilicates/ethanol solution is added dropwise, wherein tetraethyl orthosilicate/second
Tetraethyl orthosilicate, the volume ratio of ethanol are 1 in alcoholic solution：(3-5), continue the heating stirring 25-35min in 55-65 DEG C of oil bath；
Then 280-320mg dopamine hydrochlorides, the 180-220mL trishydroxymethylaminomethane aqueous solution, the trihydroxy methyl ammonia are added
The molar concentration of trishydroxymethylaminomethane is 0.5-1.2mol/L in the methylmethane aqueous solution, continues to add in 55-65 DEG C of oil bath
Thermal agitation 10-14h, is collected in the presence of externally-applied magnetic field, is cleaned with water, then is cleaned with acetone, finally the vacuum at 45-55 DEG C
5-15h is dried, obtains ferroso-ferric oxide@silica@Dopamine hydrochlorides；Take 90-110mg ferroso-ferric oxide@silica@salt
Sour dopamine adds 35-45mLN, in dinethylformamide, adds 75-80mg ZrCl4With 8-12mg terephthalic acid (TPA)s,
15-25min is heated under the conditions of 130-150 DEG C, is collected in the presence of externally-applied magnetic field, then is cleaned successively with water and methanol, in 45-
5-15h is dried in vacuo at 55 DEG C, obtains ferroso-ferric oxide@silica@Dopamine hydrochloride@zirconiums.
7. the quick determination method that Multiple Pesticides remain in blueberry as claimed in claim 6, it is characterised in that：The quaternary ammonium salt
For cetyl trimethylammonium bromide and/or lauryl trimethyl ammonium bromide.
8. the quick determination method that Multiple Pesticides remain in blueberry as claimed in claim 2, it is characterised in that：The step
(3) number of cleaning is 2-3 times in, and the dosage of each rinse water is 1-3mL.
9. the quick determination method that Multiple Pesticides remain in blueberry as claimed in claim 2, it is characterised in that：It is described quantitative interior
The acetonitrile solution of 2,4,6- tri- bromo biphenyls is designated as, wherein the concentration of 2,4,6- tri- bromo biphenyls is 0.9-1.1mg/mL；It is described quantitative
Interior target addition is 8-12 μ L.
10. the quick determination method that Multiple Pesticides remain in blueberry as claimed in claim 2, it is characterised in that：The tool plug
The capacity of centrifuge tube is 20-30mL.
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| CN114544294A (en) * | 2022-03-01 | 2022-05-27 | 南通科技职业学院 | Special pesticide residue detector of edible agricultural product |
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