CN103163253A - Purification enrichment pre-treatment technology for food packaging material and container transfer pollutant bisphenol substance - Google Patents
Purification enrichment pre-treatment technology for food packaging material and container transfer pollutant bisphenol substance Download PDFInfo
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- CN103163253A CN103163253A CN2013101052827A CN201310105282A CN103163253A CN 103163253 A CN103163253 A CN 103163253A CN 2013101052827 A CN2013101052827 A CN 2013101052827A CN 201310105282 A CN201310105282 A CN 201310105282A CN 103163253 A CN103163253 A CN 103163253A
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Abstract
The invention belongs to the technical field of purification enrichment pre-treatment for food packaging material pollutant biphenol substance. The purification enrichment pre-treatment technology comprises the following steps of: activating a C18 inverse solid phase extraction small column by methanol and ultra pure water and then loading, firstly leaching with 20% of methanol aqueous solution, then eluting with methanol, drying eluate with nitrogen in a blowing manner, redissolving residue with acetonitrile, filtering, and then carrying out liquid chromatography-fluorescence detection. By adopting the pre-treatment technology provided by the invention, recovery ratio of six biphenol substances (biphenol A (BPA), biphenol B (BPB), biphenol E (BPE), biphenol F (BPF), biphenyl A diglycidyl ether (BADGE) and biphenol F diglycidyl ether (BFDGE)) is 75.92-102.10%, relative deviation is respectivel lower than 5%, and accuracy and precision are high.
Description
Technical field
The invention belongs to the purification enrichment preconditioning technique field of packaging material for food and container migration stain thing bisphenol, particularly related to a kind of purification enrichment technical method that uses the Solid-Phase Extraction bisphenol.
Background technology
Bisphenol refers to the class epoxides matter take bisphenol-A (BPA) or Bisphenol F (BPF) as feature agent structure unit, mainly comprising bisphenol-A, Bisphenol F and derivant thereof, is the important source material of making the food contact materials such as polycarbonate, epoxy coating.In actual use, these materials can move in packaged food from wrappage or container, and food is polluted.Bisphenol will cause certain toxicity to human body under low concentration, comprises acute toxicity, mutagenicity and carcinogenicity etc.Therefore, the bisphenol in monitoring food is important measures that ensure food safety.The main detection means of bisphenol is chromatographic process at present, because bisphenol content in the actual food product system is lower, generally in the tens ppb levels to hundreds of, therefore, carrying out before chromatogram detects, still needing to carry out purifying, enrichment and the pre-service such as concentrated.
At present begin to adopt solid phase extraction techniques in the pre-service of contaminant trace species.And the selection of solid phase extraction column stuffing is most important, and its adsorption effect to bisphenol is the key that concerns purifying, enrichment success or failure; Suitable leacheate can be removed some impurity, reduce disturbance; Suitable eluent is effective wash-out object, improves the recovery.Therefore, the present invention is directed to packaging material for food and container migration stain thing bisphenol, select suitable solid-phase extraction column, leacheate and eluent, reach the purpose of effective purifying and enrichment.
Summary of the invention
The object of the invention is to provide the purification enrichment preconditioning technique method of 6 kinds of bisphenols pollutants in a kind of easy, efficient packaging material for food and container.Technical scheme of the present invention is as follows:
(1) activation of solid phase extraction column: at Solid-Phase Extraction C
18Add 5mL methyl alcohol in anti-phase pillar, vacuum filtration drip washing discards efflux; Add the 5mL ultrapure water, vacuum filtration drip washing discards efflux again;
(2) loading: the solution that 100mL is contained bisphenol (bisphenol-A (BPA), bisphenol b (BPB), bis-phenol E (BPE), Bisphenol F (BPF), bisphenol A diglycidyl ether (BADGE) and Bisphenol F diglycidyl ether (BFDGE)) slowly joins in the solid phase extraction column of activation, vacuum filtration, coutroi velocity is 2mL/min approximately, discards efflux;
(3) drip washing: after the solution that contains bisphenol is all by solid phase extraction column, add the 3mL leacheate, vacuum filtration drip washing discards efflux;
(4) wash-out: add the 6mL eluent in solid phase extraction column, vacuum filtration is collected eluent to test tube;
(5) concentrated: eluent slowly blows to half-dried with nitrogen under 40 ℃, obtains half-dried residue;
(6) redissolve: add the 1mL acetonitrile in half-dried residue, shake gently test tube, to transparent;
(7) filter: transparency liquid filters with the needle type filtration device that 0.45 μ m filter membrane is housed, and collects filtrate, obtains can be used for liquid phase detection sample.
Advantage of the present invention and beneficial effect are: adopt purification enrichment preconditioning technique of the present invention, the recovery is high, and 6 kinds of bisphenols of pre-service simultaneously can be used for extensive sample detection, are suitable for standardization.
Description of drawings
Fig. 1 HPLC-FD detects the chromatogram .1-BPF of the mixed mark of 6 kinds of bis-phenol things solution; 2-BPE; 3-BPA; 4-BPB; 5-BFDGE-1; 6-BFDGE-2; 7-BFDGE-3; 8-BADGE.
Embodiment
Below in conjunction with embodiment, the present invention is described in further details, but the present invention is not limited only to following embodiment.
Embodiment 1
Adopt HPLC-FD to detect simultaneously 6 kinds of bisphenols (BPA, BPB, BPE, BPF, BADGE and BFDGE), selecting chromatographic column is Symmetry C
18(4.6 * 250mm, 5 μ m); Column temperature: 25 ℃; Sample size: 20 μ L; Mobile phase: ultrapure water and acetonitrile; The gradient elution program sees Table 1; Flow velocity: 1.0mL/min; The excitation wavelength 227nm of fluorescence detector, absorbing wavelength 313nm.
The HPLC-FD collection of illustrative plates of 6 kinds of bisphenols is seen accompanying drawing 1, and the quantitative criterion Regression Equations sees Table 2.
Table 1 condition of gradient elution
Table 2HPLC-FD detects the linear dimensions of 6 kinds of bisphenol compounds
Embodiment 2
6 kinds of bisphenols (BPA, BPB, BPE, BPF, BADGE and BFDGE) are mixed, with the ultrapure water dilution, make the concentration of each material be 100 μ g/L.With CNWBOND LC
18SPE pillar (500mg/3mL) is placed in the 100mL standard solution in the 125mL separating funnel with 5mL methyl alcohol and the activation of 5mL water, slowly introduces the SPE device, and coutroi velocity is about 2mL/min.After solution is all by pillar, with 10mL ultrapure water drip washing separating funnel.Then, with 3mL20% methanol solution drip washing SPE pillar.Divide with 6mL methyl alcohol at last to drip the wash-out object 2 times, eluent is collected into the 10mL test tube, slowly dries up in 40 ℃ of lower nitrogen, again with 1mL acetonitrile redissolution residue, filter acetonitrile solution with 0.45 μ m PTFE pin type filter, carry out HPLC-FD and detect, condition determination such as embodiment 1.The checking recovery and standard deviation (R.S.D) are completed 3 parallel laboratory tests.Analysis result sees Table 3.
As shown in Table 3, the recovery of 6 kinds of bisphenols is between 95.43%～102.10%, and relative standard deviation is all lower than 5%, and veracity and precision is good.
The veracity and precision of table 36 kinds of bis-phenol things of enriching and purifying from ultrapure water
Embodiment 3
6 kinds of bisphenols (BPA, BPB, BPE, BPF, BADGE and BFDGE) are mixed, with 3% acetic acid solution dilution, make the concentration of each material be respectively 20 μ g/L, 50 μ g/L, 100 μ g/L.With CNWBOND LC
18SPE pillar (500mg/3mL) is placed in 100 above-mentioned variable concentrations 3% acetic acid solutions of mL in the 125mL separating funnel with 5mL methyl alcohol and the activation of 5mL water, slowly introduces the SPE device, and coutroi velocity is about 2mL/min.After solution is all by pillar, with 10mL ultrapure water drip washing separating funnel.Then, with 3mL20% methanol solution drip washing SPE pillar.Divide with 6mL methyl alcohol at last to drip the wash-out object 2 times, eluent is collected into the 10mL test tube, slowly dries up in 40 ℃ of lower nitrogen, again with 1mL acetonitrile redissolution residue, filter acetonitrile solution with 0.45 μ m PTFE pin type filter, carry out HPLC-FD and detect, condition determination such as embodiment 1.Measure the recovery and relative standard deviation (R.S.D), complete 3 parallel laboratory tests.Analysis result sees Table 4.
As shown in Table 4, the recovery of 6 kinds of bisphenols is 87.16%～98.28%, and relative standard deviation is all lower than 5%, and veracity and precision is good.
The veracity and precision of table 4 enriching and purifying bis-phenol thing from 3% acetic acid solution
Embodiment 4
6 kinds of bisphenols (BPA, BPB, BPE, BPF, BADGE and BFDGE) are mixed, with 10% ethanolic solution dilution, make the concentration of each material be respectively 20 μ g/L, 50 μ g/L, 100 μ g/L.With CNWBOND LC
18SPE pillar (500mg/3mL) is placed in above-mentioned variable concentrations 10% ethanolic solution of 100mL in the 125mL separating funnel with 5mL methyl alcohol and the activation of 5mL water, slowly introduces the SPE device, and coutroi velocity is about 2mL/min.After solution is all by pillar, with 10mL ultrapure water drip washing separating funnel.Then, with 3mL20% methanol solution drip washing SPE pillar.
The veracity and precision of table 5 enriching and purifying bis-phenol thing from 10% ethanolic solution
Divide with 6mL methyl alcohol at last to drip the wash-out object 2 times, eluent is collected into the 10mL test tube, slowly dries up in 40 ℃ of lower nitrogen, again with 1mL acetonitrile redissolution residue, filter acetonitrile solution with 0.45 μ m PTFE pin type filter, carry out HPLC-FD and detect, condition determination such as embodiment 1.Measure the recovery and relative standard deviation (R.S.D), complete 3 parallel laboratory tests.Analysis result sees Table 5.
As shown in Table 5, the recovery of 6 kinds of bisphenols in 10% ethanolic solution is 88.29%～98.29%, and relative standard deviation is all lower than 5%, and veracity and precision is good.
Embodiment 5
6 kinds of bisphenols (BPA, BPB, BPE, BPF, BADGE and BFDGE) are mixed, with the olive oil dilution, make the concentration of each material be respectively 20 μ g/L, 50 μ g/L, 100 μ g/L.
The veracity and precision of table 6 enriching and purifying bis-phenol thing from olive oil
The 500mL ether is joined in the olive oil that above-mentioned 100mL is mixed with bisphenol, and 55 ℃ of refluxing extraction 6h in 40 ℃ of lower rotary evaporated to dryness, then redissolve above-mentioned half dry with the 100mL ultrapure water with ether, obtain the bisphenol extract.With CNWBOND LC
18SPE pillar (500mg/3mL) is placed in 100mL said extracted liquid in the 125mL separating funnel with 5mL methyl alcohol and the activation of 5mL water, slowly introduces the SPE device, and coutroi velocity is about 2mL/min.After solution is all by pillar, with 10mL ultrapure water drip washing separating funnel.Then, with 3mL20% methanol solution drip washing SPE pillar.Divide with 6mL methyl alcohol at last to drip the wash-out object 2 times, eluent is collected into the 10mL test tube, slowly dries up in 40 ℃ of lower nitrogen, again with 1mL acetonitrile redissolution residue, filter acetonitrile solution with 0.45 μ m PTFE pin type filter, carry out HPLC-FD and detect, condition determination such as embodiment 1.Measure the recovery and relative standard deviation (R.S.D), complete 3 parallel laboratory tests.Analysis result sees Table 6.
As shown in Table 6, the recovery of 6 kinds of bisphenols in olive oil is 75.92%～85.85%, and relative standard deviation is all lower than 5%, and veracity and precision is better.
Above preferred embodiment only is used for illustrating content of the present invention; in addition; the present invention also has other embodiments; in every case those skilled in the art are because of technology enlightenment involved in the present invention, replace or technical scheme that the equivalent deformation mode forms all drops in protection scope of the present invention and adopt to be equal to.
Claims (5)
1. the purification enrichment preconditioning technique of a packaging material for food and container migration stain thing bisphenol, is characterized in that: comprise the steps:
(1) activation of solid phase extraction column: add 5mL methyl alcohol in solid phase extraction column, vacuum filtration drip washing discards efflux; Add the 5mL ultrapure water, vacuum filtration drip washing discards efflux again;
(2) loading: the solution that 100mL is contained bisphenol slowly joins in the solid phase extraction column of activation, vacuum filtration, and coutroi velocity is 2mL/min approximately, discards efflux;
(3) drip washing: after the solution that contains bisphenol is all by solid phase extraction column, add the 3mL leacheate, vacuum filtration drip washing discards efflux;
(4) wash-out: add the 6mL eluent in solid phase extraction column, vacuum filtration is collected eluent to test tube;
(5) concentrated: eluent slowly blows to half-dried with nitrogen under 40 ℃, obtains half-dried residue;
(6) redissolve: add the 1mL acetonitrile in half-dried residue, shake gently test tube, to transparent;
(7) filter: transparency liquid filters with the needle type filtration device that 0.45 μ m filter membrane is housed, and collects filtrate, obtains can be used for liquid phase detection sample.
2. the purification enrichment preconditioning technique of a kind of packaging material for food according to claim 1 and container migration stain thing bisphenol, it is characterized in that: the bisphenol that relates to is bisphenol-A (BPA), bisphenol b (BPB), bis-phenol E (BPE), Bisphenol F (BPF), bisphenol A diglycidyl ether (BADGE) and Bisphenol F diglycidyl ether (BFDGE).
3. the purification enrichment preconditioning technique of a kind of packaging material for food according to claim 1 and container migration stain thing bisphenol, it is characterized in that: the solid phase extraction column of selecting in described step (1)-(4) is C
18Anti-phase pillar.
4. the purification enrichment preconditioning technique of a kind of packaging material for food according to claim 1 and container migration stain thing bisphenol, it is characterized in that: the leacheate of selecting in described step (3) is 20% methanol aqueous solution.
5. the purification enrichment preconditioning technique of a kind of packaging material for food according to claim 1 and container migration stain thing bisphenol, it is characterized in that: the eluent of selecting in described step (4) is methyl alcohol.
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Cited By (6)
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| CN103837614A (en) * | 2014-02-18 | 2014-06-04 | 上海安谱科学仪器有限公司 | Method for determining migration amounts of bisphenol substances |
| CN105823850A (en) * | 2016-05-24 | 2016-08-03 | 内蒙古蒙牛乳业（集团）股份有限公司 | Method for detecting content of bisphenol A in coiled material sample |
| CN105929076A (en) * | 2016-05-24 | 2016-09-07 | 内蒙古蒙牛乳业（集团）股份有限公司 | Method for detecting content of bisphenol A in measuring spoon samples |
| CN106770787A (en) * | 2017-01-13 | 2017-05-31 | 中国农业科学院兰州畜牧与兽药研究所 | The extraction and purification methods of [4 (oxidation glycidol) phenyl] methane two in a kind of milk sample |
| CN109633069A (en) * | 2019-01-25 | 2019-04-16 | 云南省农业科学院农产品加工研究所 | Method that is a kind of while measuring three kinds of bisphenol contents |
| CN109655554A (en) * | 2019-01-26 | 2019-04-19 | 谱尼测试集团股份有限公司 | A method of measurement bis- (4- the hydroxy phenyl) -4- methylpentane contents of 2,2- |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103837614A (en) * | 2014-02-18 | 2014-06-04 | 上海安谱科学仪器有限公司 | Method for determining migration amounts of bisphenol substances |
| CN103837614B (en) * | 2014-02-18 | 2015-10-07 | 上海安谱实验科技股份有限公司 | A kind of method measuring bisphenol migration amount |
| CN105823850A (en) * | 2016-05-24 | 2016-08-03 | 内蒙古蒙牛乳业（集团）股份有限公司 | Method for detecting content of bisphenol A in coiled material sample |
| CN105929076A (en) * | 2016-05-24 | 2016-09-07 | 内蒙古蒙牛乳业（集团）股份有限公司 | Method for detecting content of bisphenol A in measuring spoon samples |
| CN106770787A (en) * | 2017-01-13 | 2017-05-31 | 中国农业科学院兰州畜牧与兽药研究所 | The extraction and purification methods of [4 (oxidation glycidol) phenyl] methane two in a kind of milk sample |
| CN109633069A (en) * | 2019-01-25 | 2019-04-16 | 云南省农业科学院农产品加工研究所 | Method that is a kind of while measuring three kinds of bisphenol contents |
| CN109633069B (en) * | 2019-01-25 | 2021-04-02 | 云南省农业科学院农产品加工研究所 | Method for simultaneously determining contents of three bisphenols |
| CN109655554A (en) * | 2019-01-26 | 2019-04-19 | 谱尼测试集团股份有限公司 | A method of measurement bis- (4- the hydroxy phenyl) -4- methylpentane contents of 2,2- |
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Application publication date: 20130619 |