CN104483433B - A kind of measure the method for bis-phenol-S in daily necessities - Google Patents
A kind of measure the method for bis-phenol-S in daily necessities Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 17
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 168
- 239000000243 solution Substances 0.000 claims abstract description 68
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 46
- 238000001819 mass spectrum Methods 0.000 claims abstract description 32
- 239000000126 substance Substances 0.000 claims abstract description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000004033 plastic Substances 0.000 claims abstract description 16
- 229920003023 plastic Polymers 0.000 claims abstract description 16
- 238000004811 liquid chromatography Methods 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims abstract description 11
- 239000003960 organic solvent Substances 0.000 claims abstract description 8
- 239000007864 aqueous solution Substances 0.000 claims abstract description 7
- 239000000523 sample Substances 0.000 claims description 140
- 150000002500 ions Chemical class 0.000 claims description 53
- 238000000605 extraction Methods 0.000 claims description 32
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 18
- 239000007791 liquid phase Substances 0.000 claims description 17
- 238000005336 cracking Methods 0.000 claims description 14
- 239000012071 phase Substances 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 11
- 239000012141 concentrate Substances 0.000 claims description 10
- 238000000132 electrospray ionisation Methods 0.000 claims description 9
- 238000002414 normal-phase solid-phase extraction Methods 0.000 claims description 9
- 238000005070 sampling Methods 0.000 claims description 9
- 239000007921 spray Substances 0.000 claims description 9
- 238000010790 dilution Methods 0.000 claims description 7
- 239000012895 dilution Substances 0.000 claims description 7
- 239000003480 eluent Substances 0.000 claims description 7
- 238000003808 methanol extraction Methods 0.000 claims description 7
- 239000012488 sample solution Substances 0.000 claims description 6
- 238000012546 transfer Methods 0.000 claims description 6
- 230000004913 activation Effects 0.000 claims description 5
- 238000001228 spectrum Methods 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 238000012856 packing Methods 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 claims description 3
- WGLUMOCWFMKWIL-UHFFFAOYSA-N dichloromethane;methanol Chemical compound OC.ClCCl WGLUMOCWFMKWIL-UHFFFAOYSA-N 0.000 claims description 2
- 239000000945 filler Substances 0.000 claims 2
- 239000002904 solvent Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 14
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 abstract description 13
- 230000014759 maintenance of location Effects 0.000 abstract description 9
- 239000000284 extract Substances 0.000 abstract description 8
- 238000003556 assay Methods 0.000 abstract description 3
- 238000001514 detection method Methods 0.000 abstract description 3
- 238000000638 solvent extraction Methods 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 2
- 238000001704 evaporation Methods 0.000 abstract description 2
- 230000008020 evaporation Effects 0.000 abstract description 2
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 abstract 1
- 238000009835 boiling Methods 0.000 description 12
- 239000000123 paper Substances 0.000 description 6
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 5
- 238000004949 mass spectrometry Methods 0.000 description 5
- 238000010812 external standard method Methods 0.000 description 4
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 description 4
- 238000005374 membrane filtration Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 238000002390 rotary evaporation Methods 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000004753 textile Substances 0.000 description 3
- 238000002137 ultrasound extraction Methods 0.000 description 3
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 229940106691 bisphenol a Drugs 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920001568 phenolic resin Polymers 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000003026 anti-oxygenic effect Effects 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 239000002781 deodorant agent Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 229940011871 estrogen Drugs 0.000 description 1
- 239000000262 estrogen Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 210000003494 hepatocyte Anatomy 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000001226 reprecipitation Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 230000004936 stimulating effect Effects 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- -1 woodwork Substances 0.000 description 1
Landscapes
- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
Abstract
The present invention relates to a kind of measure the method for bisphenol S in daily necessities, its determination step is, 1) and learn from else's experience and pulverize and the sample of mix homogeneously, add organic solvent extraction, extract molten rotated evaporation and concentration, be diluted constant volume with first alcohol and water；2) for plastic and woodwork sample, concentrated and methanol-water constant volume extracting solution HLB pillar is purified；3) liquid chromatography mass combined instrument determination step 1 is used) or 2) amount of bisphenol S in the methanol aqueous solution of gained；4) by comparing characteristic ion and abundance ratio in sample and standard substance retention time and full scan mass spectrum, whether confirmatory sample contains bisphenol S, finally according to step 3) amount of the bisphenol S of gained, calculate the content of bisphenol S in sample after conversion；The present invention not only assay method quickly, simply, and is capable of the Accurate Determining of bisphenol S content in various material daily necessities, and its detection limit is all up to 0.1mg/kg.
Description
[technical field]
The invention belongs to technical field of analytical chemistry, a kind of measure the side of bis-phenol-S in daily necessities
Method.
[background technology]
Bis-phenol-S i.e. 4,4 '-dihydroxydiphenylsulisomer, phenol and sulfuric acid reaction obtain, its No. CAS is 80-09-1.Its point
Containing the sulfuryl that two hydroxyls and an electrophilic are the strongest in son, so it is acid stronger than other phenols.This compound has excellent
Heat-resisting, fast light and antioxygenic property, be mainly used as color fixing agent, the most also can with solution additive, leather retanning agent, dispersion dye
The material dispersant of high-temperature dyeing, phenolic resin hardening accelerator, resin fire retardant etc., it is also pesticide, dyestuff, auxiliary agent simultaneously
Intermediate.As the succedaneum of bisphenol-A, bisphenol S can be as Merlon, epoxy resin, polyester, the raw material of phenolic resin and poly-
Sulfone, the raw material of polyether sulfone.Additionally, bisphenol S can be additionally used in manufacture color photographic materials, photograph contrast enhancement agents, thermal photography material
Material (developer), daily surfactant and high-efficiency deodorant etc..
The scientist in european union research center finds in investigation, and bisphenol S is similar to the toxicity of bisphenol-A, same to human body
There is the risk stimulating estrogen and causing hepatocyte to be poisoned in sample.Bisphenol S in Japan and Korea S's clear stipulaties food simulants
Migration amount must not exceed 0.05mg/L, European Union plastics regulation (EU) No.10/2011 and China's " food containers, packaging material use
Additive use sanitary standard " (GB 9685-2008) all specify bisphenol S in food simulants migration limitation be 0.05mg/
kg。
Wei Bao inspection center of Changzhou inspection and quarantine bureau develops the detection method of bisphenol S in food simulants, but how to examine
The content of the bis-phenol-S in survey product itself, thus the bis-phenol-S injury to human health is prevented from source, the most relevant report
Road.
[summary of the invention]
Present invention aim to, for different daily necessities, set up extraction, purification and the liquid of a kind of bis-phenol-S
Phase chromatograph-mass spectrometer assay method, prevents the daily necessities containing bis-phenol-S from consumer health is caused bad shadow from source
Ring.
Design for achieving the above object and a kind of measure the method for bis-phenol-S in daily necessities, comprise the following steps:
1) sample pretreatment: by the sample comminution in addition to plastic, woodwork mix homogeneously, weighs appropriate, adds
Enter organic solvent and sample is carried out supersound extraction, sample extraction solution Rotary Evaporators is concentrated, and uses first alcohol and water
It is diluted and constant volume；
2) liquid chromatography mass combined instrument determination step 1 is used) whether the solution of gained contains bis-phenol-S: if liquid phase color
When spectrum mass spectrum selects ion scan result display sample doubtful containing bis-phenol-S, then compare sample and bis-phenol-S standard substance from
Sub-full scan mass spectrum, whether to contain bis-phenol-S in confirmatory sample, the condition determination of liquid chromatography mass combined instrument is:
(1) liquid-phase chromatographic column uses Extend C18 liquid-phase chromatographic column, and specification is column length 100mm, and column internal diameter 2.1mm fills out
Material particle diameter 3.5mm；
(2) flowing is first alcohol and water mutually, and its mixed proportion is methanol: water=35:65, and the operation time is 10min；Flowing phase
Flow velocity is 0.3mL/min, and sampling volume is 10 μ L, and chromatogram column temperature is 28 DEG C；
(3) mass spectrum ionization source uses electrospray ionization source, and negative mode ionizes, and spray needle pressure is 35psi, and dry temperature is
300 DEG C, dry gas stream speed is 10L/min, and capillary voltage is 3000V；Gather and select full scan and select ion scan simultaneously
The pattern carried out, full scan scope is m/z50～300, and cracking voltage is 270V；Ion scan is selected to select ion to be m/z
249, cracking voltage is 190V；
3) if containing bis-phenol-S in confirmatory sample, then the content of bis-phenol-S in sample is calculated by formula.
Step 1) in, add methanol supersound extraction in the sample and obtain sample solution, by methanol extraction solution rotary evaporation
Instrument concentrates, and controlling pressure therebetween is 300bar, and bath temperature is 70 DEG C, and the solution after transfer concentration, to volumetric flask, uses first
Alcohol constant volume, then take this methanol solution, dilute with water constant volume.
Step 2) in, in the ion full scan mass spectrum of sample, concern as to whether the feature containing bis-phenol-S standard substance
Ion m/z 249, m/z 156, m/z 108, m/z 92, and compare they abundance ratios in the sample whether with bis-phenol-S standard
In material identical, when in sample chromatogram figure bis-phenol-S location gained chromatographic peak containing above-mentioned whole 4 characteristic ions, and abundance ratio with
When bis-phenol-S standard substance is identical, then containing bis-phenol-S in confirmatory sample.
The method of bis-phenol-S in another kind of mensuration daily necessities, comprises the following steps:
1) sample pretreatment: by plastic or the sample comminution of woodwork mix homogeneously, weighs appropriate, adds organic
Solvent carries out supersound extraction to sample, is concentrated by sample extraction solution Rotary Evaporators, and carries out dilute with first alcohol and water
Release and constant volume；
2) Solid phase extraction: use preactivated hydrophile-lipophile balance solid phase extraction column to step 1) sample of gained
Product extracting solution purifies, eluent dilute with water and constant volume；
3) liquid chromatography mass combined instrument determination step 2 is used) whether the solution of gained contains bis-phenol-S: if liquid phase color
When spectrum mass spectrum selects ion scan result display sample doubtful containing bis-phenol-S, then compare sample and bis-phenol-S standard substance from
Sub-full scan mass spectrum, whether to contain bis-phenol-S in confirmatory sample, the condition determination of liquid chromatography mass combined instrument is:
(1) liquid-phase chromatographic column uses Extend C18 liquid-phase chromatographic column, and specification is column length 100mm, and column internal diameter 2.1mm fills out
Material particle diameter 3.5mm；
(2) flowing is first alcohol and water mutually, and its mixed proportion is methanol: water=35:65, and the operation time is 10min；Flowing phase
Flow velocity is 0.3mL/min, and sampling volume is 10 μ L, and chromatogram column temperature is 28 DEG C；
(3) mass spectrum ionization source uses electrospray ionization source, and negative mode ionizes, and spray needle pressure is 35psi, and dry temperature is
300 DEG C, dry gas stream speed is 10L/min, and capillary voltage is 3000V；Gather and select full scan and select ion scan simultaneously
The pattern carried out, full scan scope is m/z50～300, and cracking voltage is 270V；Ion scan is selected to select ion to be m/z
249, cracking voltage is 190V；
4) if containing bis-phenol-S in confirmatory sample, then the content of bis-phenol-S in sample is calculated by formula.
Step 1) in, when sample is plastic, with dichloromethane, sample is carried out supersound extraction, after cooling to sample
Solution is added dropwise over methanol, to precipitate high polymer, then dichloro methane-methanol Rotary Evaporators is concentrated, its
Between to control pressure be 300bar, bath temperature is 70 DEG C, transfer concentrate after solution to volumetric flask, by methanol constant volume, then take this
Methanol solution, dilute with water constant volume.
Step 1) in, when sample is woodwork, adds methanol supersound extraction in the sample and obtain sample solution, by methanol extraction
Solution Rotary Evaporators concentrates, and controlling pressure therebetween is 300bar, and bath temperature is 70 DEG C, the solution after transfer concentration
To volumetric flask, by methanol constant volume, then take this methanol solution, dilute with water constant volume.
Step 2) in, will be by step 1) the sample extraction solution that obtains adds in advance through the hydrophilic and oleophilic of first alcohol and water activation
Balance solid phase extraction column, carries out drip washing with 50% methanol aqueous solution, and bis-phenol-S by eluting on little column packing, is washed by again with methanol
De-liquid water is diluted and constant volume.
Step 3) in, in the ion full scan mass spectrum of sample, concern as to whether the feature containing bis-phenol-S standard substance
Ion m/z 249, m/z 156, m/z 108, m/z 92, and compare they abundance ratios in the sample whether with bis-phenol-S standard
In material identical, when in sample chromatogram figure bis-phenol-S location gained chromatographic peak containing above-mentioned whole 4 characteristic ions, and abundance ratio with
When bis-phenol-S standard substance is identical, then containing bis-phenol-S in confirmatory sample.
The present invention compared with the existing technology, have the beneficial effect that the present invention be a kind of sample by organic solvent extraction, through solid phase
Extracting and purifying, uses liquid chromatography mass combined instrument to measure the method for bis-phenol-S in daily necessities, not only assay method quickly,
Simply, and it is capable of various material sample, such as the standard of bis-phenol-S content in plastic, woodwork, paper products, textile
Really measuring, create the method qualitative and quantitative for bis-phenol-S in unlike material, for unlike material, detection limit all can reach
0.1mg/kg。
[accompanying drawing explanation]
Fig. 1 is the liquid chromatogram of bis-phenol-S in embodiment 1；
Fig. 2 is the mass spectrum of bis-phenol-S in embodiment 2.
[detailed description of the invention]
The invention belongs to the mensuration of bis-phenol-S in daily necessities in analytical chemistry field, these daily necessities include moulding
Material products, paper products, woodwork and textile etc., its principle is: by the bis-phenol-S organic solvent extraction in sample, through solid phase
Extract little column purification, then measured content by liquid chromatography mass combined instrument, by comparing the full scan matter of sample and standard substance
Testing result is confirmed by chromatogram characteristic ion and abundance ratio.
In the present invention, the condition determination of liquid chromatography mass combined instrument is:
1) liquid-phase chromatographic column uses Extend C18 liquid-phase chromatographic column, and specification is column length 100 millimeters, column internal diameter 2.1 millimeters,
Packing material size 3.5 microns；
2) flowing is first alcohol and water mutually, and its mixed proportion is methanol: water=35:65, and the operation time is 10 minutes；Flowing phase
Flow velocity is 0.3mL/min, and sampling volume is 10 μ L, and chromatogram column temperature is 28 DEG C；
3) mass spectrum ionization source uses electrospray ionization source, and negative mode ionizes, and spray needle pressure is 35psi, and dry temperature is 300
DEG C, dry gas stream speed is 10L/min, and capillary voltage is 3000V.Gather and select full scan and select ion scan to carry out simultaneously
Pattern, full scan scope is m/z 50～300, and cracking voltage is 270V；Ion scan is selected to select ion to be m/z 249,
Cracking voltage is 190V.
The method of bis-phenol-S in mensuration daily necessities of the present invention, comprises the following steps:
1) sample pretreatment: sample is ground into suitable instrument the fritter of 2mm × 2mm × 2mm.Weigh appropriate pulverizing
And the sample of mix homogeneously, add organic solvent and sample is carried out supersound extraction.For plastic, must be to molten after supersound extraction
Liquid adds another kind of organic solvent, to precipitate high polymer therein.Sample extraction solution Rotary Evaporators concentrates, and
It is diluted and constant volume with first alcohol and water；
2) Solid phase extraction: for plastic and woodwork, uses hydrophile-lipophile balance (HLB) solid phase extraction column
The sample extracting solution of concentrated constant volume is purified by (HLB pillar).Will be by determination step 1) the sample extraction solution that obtains, add
Enter in advance through the HLB pillar of first alcohol and water activation, with 50% methanol aqueous solution, impurity is carried out drip washing, drain under slightly higher pressure
After pillar, with methanol by bis-phenol-S by eluting on pillar.The eluent dilute with water collected and constant volume；
3) liquid chromatography mass combined instrument determination step 1 is used) or 2) content of bis-phenol-S in the solution of gained；Work as liquid phase
When chromatographic mass spectrometry selects ion scan result display sample doubtful containing bis-phenol-S, sample and bis-phenol-S standard substance need to be compared
Ion full scan mass spectrum, with the compound whether-S as bis-phenol measured by confirming.If containing bis-phenol-S in confirmatory sample, then leading to
Cross formula and calculate the content of bis-phenol-S in sample.
Above-mentioned steps 1) in, when sample is plastic, weighs and pulverize and the sample of mix homogeneously, add dichloromethane,
35 DEG C of water bath sonicator extract 30 minutes, are transferred to after cooling in boiling flask.Extract by a small amount of dichloromethane washing sample and use
Container, cleaning mixture is incorporated in boiling flask.Shaking limit, limit is added dropwise over 100mL methanol in boiling flask, makes plastics reprecipitation.
Using Rotary Evaporators to concentrate this solution to about 5mL, controlling pressure therebetween is 300bar, and bath temperature is 70 DEG C.After concentrating
Solution be transferred to volumetric flask, and be settled to 10mL with methanol dilution.Pipette the solution after 2mL constant volume, dilute with water constant volume
To 10mL.
Above-mentioned steps 1) in, when sample is woodwork, paper products and textile etc., weighs and pulverize and the examination of mix homogeneously
Sample, addition methanol, at room temperature supersound extraction 2 times, each 30 minutes.United extraction liquid, uses Rotary Evaporators by extracting solution
Being concentrated into about 5mL, controlling pressure therebetween is 300bar, and bath temperature is 70 DEG C.This solution is shifted, and uses methanol dilution constant volume
To 10mL.Pipetting the solution after 2mL constant volume, dilute with water is also settled to 10mL.
Above-mentioned steps 2) in, when sample is plastics and woodwork, sample extraction solution must be carried out Solid phase extraction.Depend on
HLB pillar is activated by secondary 3mL methanol and 3mL water.Will be by 1) the sample extraction solution of gained is with the flow velocity of two per second
It is added drop-wise in pillar, with the methanol aqueous solution 2mL of 50%, pillar is carried out drip washing, after draining pillar under slightly higher pressure, use 3mL
Methanol-eluted fractions.With water the eluent of collection diluted and be settled to 10mL.
Above-mentioned steps 3) in, when liquid chromatography mass selects ion scan result display sample doubtful containing bis-phenol-S,
The ion full scan mass spectrum of sample and bis-phenol-S standard substance need to be compared.In ion full scan mass spectrum, need to concern as to whether to contain
There are the characteristic ion m/z 249 of bis-phenol-S, m/z 156, m/z 108, a m/z 92, and compare they abundance ratios in the sample and be
No identical with bis-phenol-S standard substance.When sample chromatogram figure bis-phenol-S location gained chromatographic peak contains above-mentioned whole 4 features
Ion, and when abundance ratio is identical with bis-phenol-S standard substance, then really containing bis-phenol-S in confirmatory sample.By quantitative equation meter
Calculate to obtain the content of bis-phenol-S in sample.
The present invention is made further explained below below in conjunction with specific embodiment:
Embodiment 1: the mensuration of bis-phenol-S in plastic cup
1. the preparation of sample:
Plastic cup is cut into the fritter of 2mm × 2mm.Weigh the sample 1.0g of mix homogeneously, add 15mL dichloromethane,
Mix homogeneously, 35 DEG C of water bath sonicator extract 30 minutes, are transferred in 250mL boiling flask by sample solution after sample cools down.
Washing sample extraction vessel with 5mL dichloromethane, wash solution is incorporated to boiling flask.Revolve in 300bar pressure and 70 DEG C of water-baths
Turn evaporation and concentration to about 5mL.This solution is transferred in 10mL volumetric flask, divides with a small amount of methanol and wash boiling flask several times, wash
Wash solution and be incorporated to volumetric flask, and with methanol dilution constant volume to scale.Accurately pipette this methanol solution of 2mL in another 10mL volumetric flask
In, dilute with water is also settled to scale.
2. the purification of extraction solution:
Successively with 3mL methanol and 3mL water activation HLB pillar, by above-mentioned sample extraction solution with on the flow velocity of two per second
Post, carries out drip washing with the methanol aqueous solution 2mL of 50% to pillar, with 3mL methanol washes after draining pillar under slightly higher pressure
De-, collection eluent, in 10mL volumetric flask, is settled to scale with water.With 0.22 μm membrane filtration in sample introduction bottle after mixing
In, analyze with LC/MS, measure the amount of bis-phenol-S, calculate the content of bis-phenol-S in sample by formula.
3. setting instrument parameter:
1) chromatograph of liquid condition
Chromatograph of liquid: Agilent 1100
Chromatographic column: Extend C18 liquid-phase chromatographic column 2.1mm × 100mm × 3.5 μm
Flowing phase: methanol: water=35:65
Flow rate of mobile phase: 0.3mL/min
Chromatogram column temperature: 28 DEG C
Sampling volume: 10 μ L
Operation time: 10min.
2) Mass Spectrometry Conditions
Ion source: electrospray ionization source
Ionization pattern: negative mode
Acquisition mode: SCAN and SIM pattern
Spray needle pressure: 35psi
Dry temperature: 300 DEG C
Dry gas stream speed: 10L/min
Capillary voltage: 3000V
Cracking voltage: SCAN pattern is 270V；SIM pattern is 190V
Scanning ion: m/z 249
Sweep limits: m/z 50～m/z 300
The most qualitative and quantitative
1) qualitative
Comparing through the retention time of sample peak with standard substance peak, sample peak mass spectrum is compared with standard substance mass spectrum
Relatively, confirm that chromatographic peak retention time is the most consistent, characteristic ion (m/z 249, m/ in corresponding chromatographic peak correspondence full scan mass spectrum
Z 156, m/z 108, m/z 92) and abundance ratio is the most unanimously, so that it is determined that whether detect determinand in sample.
2) quantitative
Use standard curve quantified by external standard method
5. calculate
According to the content of bis-phenol-S in sample extracting solution, carry out the calculating of bis-phenol-S content in sample.
Embodiment 2: the mensuration of bis-phenol-S in wood chopsticks
1. the preparation of sample:
Wood chopsticks are cut into the fritter of 2mm × 2mm × 2mm.Weigh uniform sample 1.0g, add 20ml methanol, at room temperature
Ultrasonic extraction 30 minutes, extracts solution in 250mL boiling flask filtered by filter paper.Sample again with 20mL methanol extraction once, closes
And extracting solution.In 300bar pressure and 70 DEG C of water-baths, rotary evaporation is concentrated into about 5mL, and solution is transferred to 10mL volumetric flask
In, and with a small amount of methanol mark time washing boiling flask, wash solution is incorporated in volumetric flask, and is settled to carve with methanol dilution
Degree.Accurately pipetting this solution of 2mL in another 10mL volumetric flask, dilute with water is also settled to scale.
2. the purification of extraction solution:
Successively with 3mL methanol and 3mL water activation HLB pillar, by above-mentioned sample extraction solution with on the flow velocity of two per second
Post, carries out drip washing with the methanol aqueous solution 2mL of 50% to pillar, with 3mL methanol washes after draining pillar under slightly higher pressure
De-, collection eluent is in 10mL volumetric flask, and dilute with water is settled to scale.After mixing little in sample introduction with 0.22 μm membrane filtration
In Ping, analyze with LC/MS, measure the amount of bis-phenol-S, calculate the content of bis-phenol-S in sample by formula.
3. setting instrument parameter:
1) chromatograph of liquid condition
Chromatograph of liquid: Agilent 1100
Chromatographic column: Extend C18 liquid-phase chromatographic column, 2.1mm × 100mm × 3.5 μm
Flowing phase: methanol: water=35:65
Flow rate of mobile phase: 0.3mL/min
Chromatogram column temperature: 28 DEG C
Sampling volume: 10 μ L
Operation time: 10min.
2) Mass Spectrometry Conditions
Ion source: electrospray ionization source
Ionization pattern: negative mode
Acquisition mode: SCAN and SIM pattern
Spray needle pressure: 35psi
Dry temperature: 300 DEG C
Dry gas stream speed: 10L/min
Capillary voltage: 3000V
Cracking voltage: SCAN pattern is 270V；SIM pattern is 190V
Scanning ion: m/z 249
Sweep limits: m/z 50～m/z 300
The most qualitative and quantitative
1) qualitative
Comparing through the retention time of sample peak with standard substance peak, sample peak mass spectrum is compared with standard substance mass spectrum
Relatively, confirm that chromatographic peak retention time is the most consistent, characteristic ion (m/z 249, m/ in corresponding chromatographic peak correspondence full scan mass spectrum
Z 156, m/z 108, m/z 92) and abundance ratio is the most unanimously, so that it is determined that whether detect determinand in sample.
2) quantitative
Use standard curve quantified by external standard method
5. calculate
According to the content of bis-phenol-S in sample extracting solution, carry out the calculating of bis-phenol-S content in sample.
Embodiment 3: the mensuration of bis-phenol-S in brown cardboard
1. the preparation of sample:
Brown cardboard is cut into the fritter of 2mm × 2mm × 2mm.Weigh uniform sample 1.0g, add 20ml methanol, in room
The lower ultrasonic extraction of temperature 30 minutes, extracts solution in 250mL boiling flask filtered by filter paper.Sample is again with 20mL methanol extraction one
Secondary, united extraction liquid.In 300bar pressure and 70 DEG C of water-baths, rotary evaporation is concentrated into about 5mL, solution is transferred to 10mL and holds
In measuring bottle, and with a small amount of methanol mark time washing boiling flask, wash solution is incorporated in volumetric flask, and is settled to methanol dilution
Scale.Accurately pipette this solution of 2mL in another 10mL volumetric flask, after mixing with 0.22 μm membrane filtration in sample introduction bottle,
Analyze with LC/MS, measure the amount of bis-phenol-S, calculate the content of bis-phenol-S in sample by formula.
2. setting instrument parameter:
1) chromatograph of liquid condition
Chromatograph of liquid: Agilent 1100
Chromatographic column: Extend C18 liquid-phase chromatographic column 2.1mm × 100mm × 3.5 μm
Flowing phase: methanol: water=35:65
Flow rate of mobile phase: 0.3mL/min
Chromatogram column temperature: 28 DEG C
Sampling volume: 10 μ L
Operation time: 10min.
2) Mass Spectrometry Conditions
Ion source: electrospray ionization source
Ionization pattern: negative mode
Acquisition mode: SCAN and SIM pattern
Spray needle pressure: 35psi
Dry temperature: 300 DEG C
Dry gas stream speed: 10L/min
Capillary voltage: 3000V
Cracking voltage: SCAN pattern is 270V；SIM pattern is 190V
Scanning ion: m/z 249
Sweep limits: m/z 50～m/z 300
The most qualitative and quantitative
1) qualitative
Comparing through the retention time of sample peak with standard substance peak, sample peak mass spectrum is compared with standard substance mass spectrum
Relatively, confirm that chromatographic peak retention time is the most consistent, characteristic ion (m/z 249, m/ in corresponding chromatographic peak correspondence full scan mass spectrum
Z 156, m/z 108, m/z 92) and abundance ratio is the most unanimously, so that it is determined that whether detect determinand in sample.
2) quantitative
Use standard curve quantified by external standard method
4. calculate
According to the content of bis-phenol-S in sample extracting solution, carry out the calculating of bis-phenol-S content in sample.
Embodiment 4: the mensuration of bis-phenol-S in red cotton
1. the preparation of sample:
Red cotton is cut into the fritter of 2mm × 2mm × 2mm.Weigh uniform sample 1.0g, add 20ml methanol, in room
The lower ultrasonic extraction of temperature 30 minutes, extracts solution in 250mL boiling flask filtered by filter paper.Sample is again with 20mL methanol extraction one
Secondary, united extraction liquid.In 300bar pressure and 70 DEG C of water-baths, concentrated by rotary evaporation is to about 5mL, and solution is transferred to 10mL volumetric flask
In, and with a small amount of methanol mark time washing boiling flask, wash solution is incorporated in volumetric flask, and is settled to carve with methanol dilution
Degree.Accurately pipette this solution of 2mL in another 10mL volumetric flask, after mixing with 0.22 μm membrane filtration in sample introduction bottle, use
LC/MS analyzes, and measures the amount of bis-phenol-S, calculates the content of bis-phenol-S in sample by formula.
2. setting instrument parameter:
1) chromatograph of liquid condition
Chromatograph of liquid: Agilent 1100
Chromatographic column: Extend C18 liquid-phase chromatographic column 2.1mm × 100mm × 3.5 μm
Flowing phase: methanol: water=35:65
Flow rate of mobile phase: 0.3mL/min
Chromatogram column temperature: 28 DEG C
Sampling volume: 10 μ L
Operation time: 10min.
2) Mass Spectrometry Conditions
Ion source: electrospray ionization source
Ionization pattern: negative mode
Acquisition mode: SCAN and SIM pattern
Spray needle pressure: 35psi
Dry temperature: 300 DEG C
Dry gas stream speed: 10L/min
Capillary voltage: 3000V
Cracking voltage: SCAN pattern is 270V；SIM pattern is 190V
Scanning ion: m/z 249
Sweep limits: m/z 50～m/z 300
The most qualitative and quantitative
1) qualitative
Comparing through the retention time of sample peak with standard substance peak, sample peak mass spectrum is compared with standard substance mass spectrum
Relatively, confirm that chromatographic peak retention time is the most consistent, characteristic ion (m/z 249, m/ in corresponding chromatographic peak correspondence full scan mass spectrum
Z 156, m/z 108, m/z 92) and abundance ratio is the most unanimously, so that it is determined that whether detect determinand in sample.
2) quantitative
Use standard curve quantified by external standard method
4. calculate
According to the content of bis-phenol-S in sample extracting solution, carry out the calculating of bis-phenol-S content in sample.
Claims (8)
1. one kind measures the method for bis-phenol-S in daily necessities, it is characterised in that comprise the following steps:
1) sample pretreatment: by the sample comminution in addition to plastic, woodwork mix homogeneously, weighs appropriate, there was added
Machine solvent carries out supersound extraction to sample, is concentrated by sample extraction solution Rotary Evaporators, and carries out with first alcohol and water
Dilution and constant volume；
2) liquid chromatography mass combined instrument determination step 1 is used) whether the solution of gained contains bis-phenol-S: if liquid chromatograph matter
When spectrum selects ion scan result display sample doubtful containing bis-phenol-S, then the ion comparing sample and bis-phenol-S standard substance is complete
Scanning mass spectrum, whether to contain bis-phenol-S in confirmatory sample, the condition determination of liquid chromatography mass combined instrument is:
(1) liquid-phase chromatographic column uses Extend C18 liquid-phase chromatographic column, and specification is column length 100mm, column internal diameter 2.1mm, filler grain
Footpath 3.5 μm；
(2) flowing is first alcohol and water mutually, and its mixed proportion is methanol: water=35:65, and the operation time is 10min；Flow rate of mobile phase
For 0.3mL/min, sampling volume is 10 μ L, and chromatogram column temperature is 28 DEG C；
(3) mass spectrum ionization source uses electrospray ionization source, and negative mode ionizes, and spray needle pressure is 35psi, and dry temperature is 300 DEG C,
Dry gas stream speed is 10L/min, and capillary voltage is 3000V；Gather and select full scan and select ion scan to carry out simultaneously
Pattern, full scan scope is m/z50～300, and cracking voltage is 270V；Ion scan is selected to select ion to be m/z 249, cracking
Voltage is 190V；
3) if containing bis-phenol-S in confirmatory sample, then the content of bis-phenol-S in sample is calculated by formula.
2. the method for claim 1, it is characterised in that: step 1) in, add methanol supersound extraction in the sample and obtain sample
Product solution, concentrates methanol extraction solution Rotary Evaporators, and controlling pressure therebetween is 300bar, and bath temperature is 70
DEG C, transfer concentrate after solution to volumetric flask, by methanol constant volume, then take this methanol solution, dilute with water constant volume.
3. the method for claim 1, it is characterised in that step 2) in, in the ion full scan mass spectrum of sample, close
Whether note contains the characteristic ion m/z 249 of bis-phenol-S standard substance, m/z 156, m/z 108, m/z 92, and compare they
Abundance ratio in sample is the most identical with bis-phenol-S standard substance, when containing in sample chromatogram figure bis-phenol-S location gained chromatographic peak
Above-mentioned whole 4 characteristic ions, and when abundance ratio is identical with bis-phenol-S standard substance, then containing bis-phenol-S in confirmatory sample.
4. one kind measures the method for bis-phenol-S in daily necessities, it is characterised in that comprise the following steps:
1) sample pretreatment: by plastic or the sample comminution of woodwork mix homogeneously, weighs appropriate, adds organic solvent
Sample is carried out supersound extraction, sample extraction solution Rotary Evaporators is concentrated, and be diluted with first alcohol and water and
Constant volume；
2) Solid phase extraction: use preactivated hydrophile-lipophile balance solid phase extraction column to step 1) sample of gained carries
Take liquid to purify, eluent dilute with water and constant volume；
3) liquid chromatography mass combined instrument determination step 2 is used) whether the solution of gained contains bis-phenol-S: if liquid chromatograph matter
When spectrum selects ion scan result display sample doubtful containing bis-phenol-S, then the ion comparing sample and bis-phenol-S standard substance is complete
Scanning mass spectrum, whether to contain bis-phenol-S in confirmatory sample, the condition determination of liquid chromatography mass combined instrument is:
(1) liquid-phase chromatographic column uses Extend C18 liquid-phase chromatographic column, and specification is column length 100mm, column internal diameter 2.1mm, filler grain
Footpath 3.5 μm；
(2) flowing is first alcohol and water mutually, and its mixed proportion is methanol: water=35:65, and the operation time is 10min；Flow rate of mobile phase
For 0.3mL/min, sampling volume is 10 μ L, and chromatogram column temperature is 28 DEG C；
(3) mass spectrum ionization source uses electrospray ionization source, and negative mode ionizes, and spray needle pressure is 35psi, and dry temperature is 300 DEG C,
Dry gas stream speed is 10L/min, and capillary voltage is 3000V；Gather and select full scan and select ion scan to carry out simultaneously
Pattern, full scan scope is m/z50～300, and cracking voltage is 270V；Ion scan is selected to select ion to be m/z 249, cracking
Voltage is 190V；
4) if containing bis-phenol-S in confirmatory sample, then the content of bis-phenol-S in sample is calculated by formula.
5. method as claimed in claim 4, it is characterised in that: step 1) in, when sample is plastic, with dichloromethane pair
Sample carries out supersound extraction, is added dropwise over methanol after cooling in sample solution, to precipitate high polymer, then by dichloromethane-
Methanol solution Rotary Evaporators concentrates, and controlling pressure therebetween is 300bar, and bath temperature is 70 DEG C, after transfer concentrates
Solution is to volumetric flask, by methanol constant volume, then takes this methanol solution, dilute with water constant volume.
6. method as claimed in claim 4, it is characterised in that: step 1) in, when sample is woodwork, add first in the sample
Alcohol supersound extraction obtains sample solution, is concentrated by methanol extraction solution Rotary Evaporators, and controlling pressure therebetween is 300bar,
Bath temperature is 70 DEG C, transfer concentrate after solution to volumetric flask, by methanol constant volume, then take this methanol solution, dilute with water is also
Constant volume.
7. method as claimed in claim 4, it is characterised in that: step 2) in, will be by step 1) the sample extraction solution that obtains
Add in advance through the hydrophile-lipophile balance solid phase extraction column of first alcohol and water activation, carry out drip washing with 50% methanol aqueous solution, then
With methanol, bis-phenol-S is diluted and constant volume by eluting on little column packing, eluent water.
8. method as claimed in claim 4, it is characterised in that step 3) in, in the ion full scan mass spectrum of sample, close
Whether note contains the characteristic ion m/z 249 of bis-phenol-S standard substance, m/z 156, m/z 108, m/z 92, and compare they
Abundance ratio in sample is the most identical with bis-phenol-S standard substance, when containing in sample chromatogram figure bis-phenol-S location gained chromatographic peak
Above-mentioned whole 4 characteristic ions, and when abundance ratio is identical with bis-phenol-S standard substance, then containing bis-phenol-S in confirmatory sample.
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| CN103736468A (en) * | 2014-01-16 | 2014-04-23 | 昆明理工大学 | Preparation method of dual-template molecular imprinting adsorption and extraction stirring rod |
| CN104007218A (en) * | 2014-06-06 | 2014-08-27 | 北京礼来科技发展中心 | Determination method of bisphenol S transfer volume in plastic food packaging materials |
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| JPH05279320A (en) * | 1992-04-01 | 1993-10-26 | Fuji Photo Film Co Ltd | Bisphenol compound |
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| CN103736468A (en) * | 2014-01-16 | 2014-04-23 | 昆明理工大学 | Preparation method of dual-template molecular imprinting adsorption and extraction stirring rod |
| CN104007218A (en) * | 2014-06-06 | 2014-08-27 | 北京礼来科技发展中心 | Determination method of bisphenol S transfer volume in plastic food packaging materials |
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