CN106226443A - Supermolecule solvent extraction combines the method for Magnetic solid phases extraction detection bisphenol-A class material - Google Patents
Supermolecule solvent extraction combines the method for Magnetic solid phases extraction detection bisphenol-A class material Download PDFInfo
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- CN106226443A CN106226443A CN201610837032.6A CN201610837032A CN106226443A CN 106226443 A CN106226443 A CN 106226443A CN 201610837032 A CN201610837032 A CN 201610837032A CN 106226443 A CN106226443 A CN 106226443A
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- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 239000000463 material Substances 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 title claims abstract description 26
- 238000000638 solvent extraction Methods 0.000 title claims abstract description 24
- 239000007790 solid phase Substances 0.000 title claims abstract description 22
- 238000001514 detection method Methods 0.000 title claims abstract description 18
- 238000000605 extraction Methods 0.000 title claims abstract description 17
- 239000000696 magnetic material Substances 0.000 claims abstract description 19
- 239000002904 solvent Substances 0.000 claims abstract description 17
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910001051 Magnalium Inorganic materials 0.000 claims abstract description 15
- 239000007788 liquid Substances 0.000 claims abstract description 15
- 239000002131 composite material Substances 0.000 claims abstract description 13
- 239000002184 metal Substances 0.000 claims abstract description 12
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 37
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 27
- 229910052681 coesite Inorganic materials 0.000 claims description 25
- 229910052906 cristobalite Inorganic materials 0.000 claims description 25
- 229910052682 stishovite Inorganic materials 0.000 claims description 25
- 229910052905 tridymite Inorganic materials 0.000 claims description 25
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 24
- 229940106691 bisphenol a Drugs 0.000 claims description 17
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 230000015572 biosynthetic process Effects 0.000 claims description 11
- 238000003786 synthesis reaction Methods 0.000 claims description 11
- 239000002122 magnetic nanoparticle Substances 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 238000013019 agitation Methods 0.000 claims description 9
- 239000012153 distilled water Substances 0.000 claims description 9
- 239000003480 eluent Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 239000000047 product Substances 0.000 claims description 9
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 8
- ZFVMWEVVKGLCIJ-UHFFFAOYSA-N bisphenol AF Chemical compound C1=CC(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C=C1 ZFVMWEVVKGLCIJ-UHFFFAOYSA-N 0.000 claims description 8
- -1 enanthol Chemical compound 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 8
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 claims description 7
- 229910021529 ammonia Inorganic materials 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- XSXWOBXNYNULJG-UHFFFAOYSA-N 2-(2,4,4-trimethylpentan-2-yl)phenol Chemical compound CC(C)(C)CC(C)(C)C1=CC=CC=C1O XSXWOBXNYNULJG-UHFFFAOYSA-N 0.000 claims description 3
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 3
- 239000007853 buffer solution Substances 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 150000001805 chlorine compounds Chemical class 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 238000003556 assay Methods 0.000 claims description 2
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- 239000006228 supernatant Substances 0.000 claims description 2
- 239000003643 water by type Substances 0.000 claims description 2
- JLDSOYXADOWAKB-UHFFFAOYSA-N aluminium nitrate Chemical compound [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-UHFFFAOYSA-N 0.000 claims 2
- 238000004821 distillation Methods 0.000 claims 1
- 239000007791 liquid phase Substances 0.000 claims 1
- 230000003647 oxidation Effects 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
- 239000000376 reactant Substances 0.000 claims 1
- 238000010521 absorption reaction Methods 0.000 abstract description 3
- 150000002191 fatty alcohols Chemical class 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 3
- 239000002086 nanomaterial Substances 0.000 abstract description 2
- 230000035945 sensitivity Effects 0.000 abstract description 2
- 239000006185 dispersion Substances 0.000 abstract 1
- 230000007613 environmental effect Effects 0.000 abstract 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 8
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 239000008346 aqueous phase Substances 0.000 description 4
- 238000005374 membrane filtration Methods 0.000 description 4
- 208000035126 Facies Diseases 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 238000010189 synthetic method Methods 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 238000002414 normal-phase solid-phase extraction Methods 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- ZYUVGYBAPZYKSA-UHFFFAOYSA-N 5-(3-hydroxybutan-2-yl)-4-methylbenzene-1,3-diol Chemical class CC(O)C(C)C1=CC(O)=CC(O)=C1C ZYUVGYBAPZYKSA-UHFFFAOYSA-N 0.000 description 1
- 208000007466 Male Infertility Diseases 0.000 description 1
- 208000008589 Obesity Diseases 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000000136 cloud-point extraction Methods 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 206010012601 diabetes mellitus Diseases 0.000 description 1
- FDSGHYHRLSWSLQ-UHFFFAOYSA-N dichloromethane;propan-2-one Chemical compound ClCCl.CC(C)=O FDSGHYHRLSWSLQ-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 230000002068 genetic effect Effects 0.000 description 1
- 230000003054 hormonal effect Effects 0.000 description 1
- 210000000987 immune system Anatomy 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 210000003734 kidney Anatomy 0.000 description 1
- 238000000622 liquid--liquid extraction Methods 0.000 description 1
- 210000004185 liver Anatomy 0.000 description 1
- 210000005075 mammary gland Anatomy 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 235000020824 obesity Nutrition 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000002927 oxygen compounds Chemical class 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
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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
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
- G01N2030/062—Preparation extracting sample from raw material
Landscapes
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
- Compounds Of Iron (AREA)
Abstract
The invention discloses a kind of method that supermolecule solvent extraction combines Magnetic solid phases extraction detection bisphenol-A class material, bisphenol-A class material is extracted by the supermolecule solvent that the method uses oxolane to form with fatty alcohol with magnetic magnalium di-hydroxyl composite metal oxidate, and combines its content of high-performance liquid chromatogram determination.Magnetic magnalium di-hydroxyl composite metal oxidate magnetic material good dispersion in supermolecule solvent, the absorption that bisphenol-A class material has been had, meanwhile, utilize externally-applied magnetic field sharp separation.This pre-treating method, compared with the sample-pretreating method that other is traditional, has detection sensitivity height, low cost, and simple to operate, separating rate is fast, and the repeatable utilization of magnetic Nano material, environmental protection, is with a wide range of applications.
Description
Technical field
The invention belongs to analytical chemistry field, be specifically related to a kind of supermolecule solvent extraction and combine Magnetic solid phases extraction inspection
The method surveying bisphenol-A class material.
Background technology
Bisphenol-A formal name used at school 2,2-bis-(4-hydroxy phenyl) propane, also referred to as BPA, be a kind of ectogenic incretion interferent,
It it is a kind of additive of synthetic plastic packing articles.Bisphenol-A can move to food or drink by packaging for foodstuff and plastic sheeting
In material, it is absorbed by the body, and then is progressively detrimental to health, the hormonal system immune system god of the mankind and wild animal can be made
Occur abnormal through system, also can the reproduction Genetic Function of severe jamming human and animal.Research report, bisphenol-A has female sharp
The characteristic of element, has certain damage to liver kidney mammary gland；Bisphenol-A also has with obesity diabetes and male infertility simultaneously
Close.Bisphenol-A consumption is defined as in every liter of distilled water contained bisphenol-A by the sanitary standard that China announces and is less than 0.05 mg；
Owing to bisphenol-A is very harmful, hence set up detection limit low bisphenol-A quickly and accurately detection method particularly important.
At present, the detection method of BPA content mainly has high performance liquid chromatography, gas chromatography, electrochemical process and gas phase
Chromatography mass spectrometry, HPLC MS etc..Sample pre-treatments has liquid-liquid extraction, Solid-Phase Extraction, cloud point extraction, ion
Liquid extractions etc., these extracting process suffer from respective pluses and minuses.Our research group application patent of invention " a kind of food
The method for quick of the bisphenol-A (BPA) in packaging material-Merlon (PC) material " (CN 103808815 A), disclose
BPA in supermolecule solvent extraction sample liquid, but there is also the operation of centrifugal split-phase, furthermore supermolecule solvent only separates effect
Really, not to the clean-up effect of chaff interference in sample substrate.
The present invention utilizes supermolecule solvent extraction to combine Magnetic solid phases extraction detection bisphenol-A class material, both make use of oversubscription
Sub-solvent is to the bisphenol-A preferable affinity of class material, and simultaneously synthesizing magnetic magnalium di-hydroxyl composite metal oxidate is both to double
Phenol A class material has certain absorption property, moreover it is possible to is eliminated by the interfering material in sample, utilizes supermolecule solvent and magnetic simultaneously
Property material synergic solvent extraction, not only bisphenol-A class extracting substances rate is high, utilizes additional Magnet energy sharp separation.
Summary of the invention
It is an object of the invention to provide a kind of supermolecule solvent extraction and combine Magnetic solid phases extraction detection bisphenol-A class material
Method.
It is to be come in fact by below scheme that supermolecule solvent extraction combines the method for Magnetic solid phases extraction detection bisphenol-A class material
Existing:
In the solution containing bisphenol-A class material, add supermolecule solvent, vortex mixed, add the double hydroxyl of magnetic magnalium and be combined
Metal oxide magnetic material, vortex mixed so that it is dispersed in the solution, then stand after 5～10min, use external magnetic field
Collect the solid extracting agent with object, remove supernatant, use eluent solid extracting agent, collect eluent, use
High performance liquid chromatography carries out assay.
Any one in described supermolecule solvent union alcohol, enanthol, capryl alcohol combines with oxolane, and a combination thereof ratio is
0.3-0.5: 1, compositions consumption is interpolation 0.3-0.6mL in every 10 mL sample liquid.
Described magnetic magnalium di-hydroxyl composite metal oxidate magnetic material is prepared as follows:
Fe3O4The synthesis of magnetic nano-particle: weigh 2.05 g Ferrous ammonium sulfates and 1.41 g ferric chlorides are dissolved in 50
In mL deionized water, being transferred to by mixed liquor in 250 mL there-necked flasks, the lower mechanical agitation of nitrogen protection heating in water bath, when instead
When answering liquid to be heated to 80 DEG C, adding 5 mL ammonia (28%, w/v), solution colour has brown color to immediately become black, successive reaction
Naturally cool to room temperature after 30 min, utilize additional Magnet to be separated by its product, respectively successively with appropriate ethanol and distilled water
Each washing 3 ~ 5 times, its Fe prepared the most at last3O412h it is vacuum dried at 50 DEG C, standby；
SiO2The Fe of parcel3O4The synthesis of magnetic nano-particle: the Fe of 100 mg3O4It is dispersed in 80 mL ethanol and 20 mL water
Mixed liquor in, ultrasonic agitation 30 min makes it be uniformly dispersed, and is transferred to by mixed liquor in 250 mL there-necked flasks, adjusts with ammonia
Add 0.2 mL tetraethyl orthosilicate (TEOS) after joint pH to 9, be passed through nitrogen and protect at room temperature mechanical agitation 4 h, product profit
3 ~ 5 extremely neutrality are respectively washed, then by prepared SiO with appropriate ethanol and distilled water successively after collecting with additional Magnet2Bag
The Fe wrapped up in3O4Magnetic nano-particle Fe3O4@SiO212h it is vacuum dried at 50 DEG C, standby；
Magnetic material magnetic magnalium di-hydroxyl composite metal oxidate (Fe3O4@SiO2@Mg Al LDH) synthesis: 0.1 g
Fe3O4@SiO2It is scattered in 50 mL deionized waters, and with 1.28 g Na2CO3With 1.6 g NaOH be dissolved in 100 mL methanol-
PH to 10.0 adjusted by the buffer solution that water (1:1, v/v) is formed, and is slowly added to the speed of 1 mL/min the most with vigorous stirring
20 mL contain 1.44 mmol Mg (NO3)26H2O and 0.48 mmol Al (NO3)3·9H2The aqueous solution of O, ultrasonic 1 h
After, utilize additional Magnet to be separated by its product, respectively wash 3 ~ 5 times with appropriate ethanol and distilled water the most successively, the most at last its
The magnetic material Fe prepared3O4@SiO2@Mg Al LDH is vacuum dried 12h at 50 DEG C, standby.
Described magnetic magnalium di-hydroxyl composite metal oxidate magnetic material Fe3O4 SiO2 Mg Al LDH consumption for for
Every 10 mL sample liquid are added 2 ~ 10 mg.
Described vortex time 2 ~ 6 min.
Described bisphenol-A class material include bisphenol-A, bisphenol AF, tetrabromobisphenol A, to one or more in tert-octylphenol.
Described eluant is the one in methanol, acetonitrile, oxolane, acetonitrile/oxolane (v/v=9:1), eluting
Number of times is 1 ~ 2 time, and the consumption of each eluant is 0.5 ~ 1.0 mL.
Relative to prior art, the present invention has a following remarkable advantage:
1, the present invention utilizes supermolecule solvent to the bisphenol-A preferable affinity of class material, and the double hydroxyl of the magnetic magnalium of synthesis is combined
Metal-oxide has certain absorption property to bisphenol-A class material, the two synergic solvent extraction, and not only bisphenol-A class extracting substances rate is high, profit
With additional Magnet energy sharp separation；
2, magnetic Solid-Phase Extraction is combined with supermolecule solvent extraction, can extract object, can have again purification, eliminates interference,
Collect the extractant of extraction object by external magnetic field, use suitable eluent eluting, simple to operate, quick, consumption of organic solvent pole
Little；
3, combining high performance liquid chromatography/fluorescence detector to be analyzed, detection limit is low, highly sensitive, and recovery of standard addition is high.
Accompanying drawing explanation
Fig. 1 is mark-on bisphenol-A (BPA) in embodiment 3, bisphenol AF (BPAF) and tetrabromobisphenol A (TBBPA) (100 μ g/ L)
Chromatogram；A is through supermolecule solvent extraction chromatogram；B is through supermolecule solvent and magnetic magnalium di-hydroxyl composite metal oxygen
Compound processes chromatogram.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is further described, but protection scope of the present invention is not limited to this.
Embodiment 1: the mensuration of bisphenol-A class material in infusion cover
(1) magnetic material Fe3O4@SiO2The synthesis of@Mg Al LDH
Fe3O4The synthesis of magnetic nano-particle: weigh 2.05 g Ferrous ammonium sulfates and 1.41 g ferric chlorides are dissolved in 50
In mL deionized water, being transferred to by mixed liquor in 250 mL there-necked flasks, the lower mechanical agitation of nitrogen protection heating in water bath, when instead
When answering liquid to be heated to 80 DEG C, adding 5 mL ammonia (28%, w/v), solution colour has brown color to immediately become black, successive reaction
Naturally cool to room temperature after 30 min, utilize additional Magnet to be separated by its product, respectively successively with appropriate ethanol and distilled water
Each washing 3 ~ 5 times, its Fe prepared the most at last3O412h it is vacuum dried at 50 DEG C, standby；
SiO2The Fe of parcel3O4The synthesis of magnetic nano-particle: the Fe of 100 mg3O4It is dispersed in 80 mL ethanol and 20 mL water
Mixed liquor in, ultrasonic agitation 30 min makes it be uniformly dispersed, and is transferred to by mixed liquor in 250 mL there-necked flasks, adjusts with ammonia
Add 0.2 mL tetraethyl orthosilicate (TEOS) after joint pH to 9, be passed through nitrogen and protect at room temperature mechanical agitation 4 h, product profit
3 ~ 5 extremely neutrality are respectively washed, then by prepared SiO with appropriate ethanol and distilled water successively after collecting with additional Magnet2Bag
The Fe wrapped up in3O4Magnetic nano-particle Fe3O4@SiO212h it is vacuum dried at 50 DEG C, standby；
Magnetic composite Fe3O4@SiO2The synthesis of@Mg Al LDH: 0.1 g Fe3O4@SiO2It is scattered in 50 mL deionizations
In water, and with 1.28 g Na2CO3 It is dissolved in the buffer solution tune that 100 mL methanol-waters (1:1, v/v) are formed with 1.6 g NaOH
PH to 10.0, is slowly added to 20 mL with the speed of 1 mL/min the most with vigorous stirring and contains 1.44 mmol Mg
(NO3)2·6H2O and 0.48 mmol Al (NO3)3·9H2The aqueous solution of O, after ultrasonic 1 h, utilizes additional Magnet by its product
Separate, respectively wash 3 ~ 5 times with appropriate ethanol and distilled water the most successively, its magnetic Nano material prepared the most at last
Fe3O4@SiO2@Mg Al LDH is vacuum dried 12h at 50 DEG C, standby；
(2) prepared by sample: drying in cool place after taking transfusion lid pure water rinsing, shredded by lid, precision weighs 1g(and is accurate to
0.001 g) sample, puts in beaker, adds 10mL dichloromethane, and ultrasonic (power 120W frequency 40kHz) dissolves and mix, and adds
Entering 15mL methanol, shake well, make macromolecular compound precipitate, filter, filtrate, at 40 DEG C of water bath methods, is dissolved residual with methanol
Slag, transfer is put in 10mL measuring bottle, is diluted to scale with deionized water, obtains sample liquid；
(3) sample determination: add 70 μ L capryl alcohol, the supermolecule solvent of 350 μ L oxolane compositions in step (2) sample liquid,
Vortex 2min, finally, adds 2mg magnetic material Fe3O4@SiO2@Mg Al LDH, vortex 3min, after standing balance 15min,
Collect solid phase aqueous phase discarded with Magnet, be eluant to solid phase eluting twice with 1mL acetonitrile/oxolane (v/v=9:1), collect
Eluent after 0.45 m organic facies membrane filtration with HPLC analyze, record content of bisphenol A 3.08 μ g/g.
Embodiment 2: the mensuration of bisphenol-A class material in feeding bottle
(1) magnetic material Fe3O4@SiO2The synthetic method of@Mg Al LDH is with embodiment 1；
(2) prepared by sample: weighs 0.5g(and is accurate to 0.001 g) testing sample that shreds, add 10mL dichloromethane, ultrasonic
After (power 120W frequency 40kHz) makes sample dissolve or be swelling, add 15mL methanol, shake well, make macromolecular compound sink
Forming sediment, filter, filtrate, at 40 DEG C of water bath methods, uses methanol dissolved residue, and transfer is put in 10mL measuring bottle, is diluted to carve with deionized water
Degree, obtains sample liquid；
(3) sample determination: add 105 μ L enanthol, the supermolecule solvent of 350 μ L oxolane compositions in step (2) sample liquid,
Vortex 5min；Finally, 5mg magnetic material Fe is added3O4@SiO2@Mg Al LDH, vortex 4min, after balance 5min, use Magnet
Collecting solid phase aqueous phase discarded, with 0.5mL acetonitrile for eluant to solid phase eluting twice, the eluent of collection is organic through 0.45 m
Analyze with HPLC after phase membrane filtration, record bisphenol AF content 0.58 μ g/g.
Embodiment 3: the mensuration of bisphenol-A class material in waste water
(1) magnetic material Fe3O4@SiO2The synthetic method of@Mg Al LDH is with embodiment 1；
(2) sample determination: take and add 100 μ L nonyl alcohols, the supermolecule solvent of 500 μ L oxolane compositions in 10mL wastewater sample,
Vortex 3min；Finally, 10mg magnetic material Fe is added3O4@SiO2@Mg Al, vortex 5min, after balance 10min, receive with Magnet
Collection solid phase aqueous phase discarded, with 1mL methanol for eluant to solid phase eluting twice, the eluent of collection is filtered through 0.45 m organic facies
Analyze with HPLC after membrane filtration, record content of bisphenol A 0.31 μ g/ L, tetrabromobisphenol A content 0.17 μ g/ L.
Embodiment 4: the mensuration of bisphenol-A class material in coating
(1) magnetic material Fe3O4@SiO2The synthetic method of@Mg Al LDH is with embodiment 1；
(2) prepared by sample: accurately weighs the coating sample 0.5g(stirred and is accurate to 0.001 g), it is placed in 10mL tool plug ratio
In colour tube, add 10mL dichloromethane-acetone (volume ratio 1: 1) mixed solvent, (power 120W frequency ultrasonic under room temperature
40kHz) extracting 10min, add 15mL methanol, shake well, filter, filtrate, at 40 DEG C of water bath methods, uses methanol dissolved residue,
Transfer is put in 10mL measuring bottle, is diluted to scale with deionized water, obtains sample liquid；
(3) sample determination: add 100 μ L capryl alcohol, the supermolecule solvent of 200 μ L oxolane compositions in step (2) sample liquid,
Vortex 6min；Finally, 10mg magnetic material Fe is added3O4@SiO2@Mg Al, vortex 5min, after balance 20min, receive with Magnet
Collection solid phase aqueous phase discarded, with 0.5mL ethanol for eluant to solid phase eluting twice, the eluent of collection is through 0.45 m organic facies
Analyze with HPLC after membrane filtration, record bisphenol AF content 15.2 μ g/g, to tert-octylphenol 0.12 μ g/g.
Above example compares with only measuring by supermolecule solvent extraction and the present invention, the results are shown in Table 1；
Table 1 measurement result compares (μ g/kg)
From table 1 this, the present invention uses the supermolecule solvent hydroxyl double with magnetic magnalium of oxolane and fatty alcohol composition multiple
Close metal-oxide and bisphenol-A class material is carried out extraction and the independent supermolecule solvent extraction through oxolane with fatty alcohol composition
Taking and compare, sensitivity is improved.
Fig. 1 is mark-on bisphenol-A (BPA) in embodiment 3 waste water, bisphenol AF (BPAF) and tetrabromobisphenol A (TBBPA) (100 μ
G/ L) after the chromatogram of the supermolecule solvent extraction that carries out and the inventive method contrast；A is through supermolecule solvent extraction chromatograph
Figure；B is to process chromatogram through supermolecule solvent with magnetic magnalium di-hydroxyl composite metal oxidate；As seen from Figure 1, through the present invention
Chromatogram after process has obtained good purification.
Claims (7)
1. the method that a supermolecule solvent extraction combines Magnetic solid phases extraction detection bisphenol-A class material, it is characterised in that: containing
Have in the solution of bisphenol-A class material, add supermolecule solvent, vortex mixed, add the oxidation of magnetic magnalium di-hydroxyl composite metal
Thing magnetic material, vortex mixed so that it is dispersed then stand after 5～20min in the solution, with external magnetic field collect with
The solid extracting agent of object, removes supernatant, uses eluent solid extracting agent, collects eluent, uses efficient liquid phase
Chromatograph carries out assay.
Supermolecule solvent extraction the most according to claim 1 combines the method for Magnetic solid phases extraction detection bisphenol-A class material,
It is characterized in that: any one in supermolecule solvent union alcohol, enanthol, capryl alcohol combines with oxolane, and a combination thereof ratio is
0.2-0.5: 1, compositions consumption is interpolation 0.3-0.6mL in every 10 mL sample liquid.
Supermolecule solvent extraction the most according to claim 1 combines the method for Magnetic solid phases extraction detection bisphenol-A class material,
It is characterized in that, magnetic magnalium di-hydroxyl composite metal oxidate magnetic material is prepared as follows and obtains:
Fe3O4The synthesis of magnetic nano-particle: weigh 2.05 g Ferrous ammonium sulfates and 1.41 g ferric chlorides are dissolved in 50
In mL deionized water, being transferred in there-necked flask by mixed liquor, the lower mechanical agitation of nitrogen protection heating in water bath, when reactant liquor adds
When heat is to 80 DEG C, adding ammonia, solution colour is immediately become black by brown color, naturally cools to room after successive reaction 30 min
Temperature, utilizes additional Magnet to be separated by its product, respectively washs 3 ~ 5 times with ethanol and distilled water the most successively, prepares the most at last
Fe3O4Magnetic nano-particle is vacuum dried 12h at 50 DEG C, standby；
SiO2The Fe of parcel3O4The synthesis of magnetic nano-particle: the Fe of 100 mg3O4It is dispersed in 80 mL ethanol and 20 mL water
Mixed liquor in, ultrasonic agitation 30 min makes it be uniformly dispersed, and is transferred in there-necked flask by mixed liquor, with ammonia regulation pH extremely
Adding 0.2 mL tetraethyl orthosilicate after 9, be passed through nitrogen and protect at room temperature mechanical agitation 4 h, the additional Magnet of product utilization is received
3 ~ 5 extremely neutrality are respectively washed, then by prepared SiO with ethanol and distilled water successively after collection2The Fe of parcel3O4Magnetic nano particle
Sub-Fe3O4@SiO212h it is vacuum dried at 50 DEG C, standby；
Magnetic magnalium di-hydroxyl composite metal oxidate magnetic material Fe3O4@SiO2The synthesis of@Mg Al LDH: 0.1 g
Fe3O4@SiO2It is scattered in 50 mL deionized waters, and with 1.28 g Na2CO3With 1.6 g NaOH be dissolved in 100 mL methanol-
The buffer solution formed in aqueous solution adjusts pH to 10.0, wherein methanol in methanol-water solution: water volume ratio is 1:1；Then in play
It is slowly added to 20 mL with the speed of 1 mL/min under strong stirring and contains 1.44 mmol Mg (NO3)2·6H2O and 0.48 mmol
Al(NO3)3·9H2The aqueous solution of O, after ultrasonic 1 h, utilizes additional Magnet to be separated by its product, the most successively with ethanol and distillation
Water respectively washs 3 ~ 5 times, the magnetic material Fe prepared the most at last3O4@SiO2@Mg Al LDH is vacuum dried at 50 DEG C
12h, standby.
Supermolecule solvent extraction the most according to claim 3 combines the method for Magnetic solid phases extraction detection bisphenol-A class material,
It is characterized in that: magnetic magnalium di-hydroxyl composite metal oxidate magnetic material Fe3O4 SiO2 Mg Al LDH consumption is every 10
ML sample liquid is added 2 ~ 10 mg.
Supermolecule solvent extraction the most according to claim 1 combines the method for Magnetic solid phases extraction detection bisphenol-A class material,
It is characterized in that: vortex time is 2 ~ 6min.
Supermolecule solvent extraction the most according to claim 1 combines the method for Magnetic solid phases extraction detection bisphenol-A class material,
It is characterized in that: bisphenol-A class material include bisphenol-A, bisphenol AF, tetrabromobisphenol A, to one or more in tert-octylphenol.
Supermolecule solvent extraction the most according to claim 1 combines the method for Magnetic solid phases extraction detection bisphenol-A class material,
It is characterized in that: eluant is the one in methanol, acetonitrile, oxolane, acetonitrile/oxolane mixed liquor, and washing steps is 1
~ 2 times, the consumption of each eluant is 0.5 ~ 2.0 mL, wherein acetonitrile and the body of oxolane in acetonitrile/oxolane mixed liquor
Long-pending ratio is 9:1.
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