CN105021754A - Liquid chromatography-tandem mass spectrometry method for simultaneous determination of specific migration of 18 phenols or phenol derivatives in five plastic food simulants - Google Patents
Liquid chromatography-tandem mass spectrometry method for simultaneous determination of specific migration of 18 phenols or phenol derivatives in five plastic food simulants Download PDFInfo
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Abstract
The present invention provides a high performance liquid chromatography-tandem mass spectrometry method for simultaneous determination of specific migration of 18 phenols or phenol derivatives in five plastic food simulants. The method is as below: soaking a sample to be measured in food simulants, cooling to room temperature, mixing well, filtering a water-based soaking liquid by a PTFE syringe needle filter; t extracting vegetable food simulant with acetonitrile, and filtering the supernatant by a PTFE needle filter, and introducing sample; eluting and separating by a C8 column; and running under negative multiple reaction monitoring mode by using a mass spectrometry with electro-spray ionization source. The method has good chromatographic separation, linear relationship, high recovery and accuracy, meets limited requirements of 18 phenols or phenol derivatives in EU regulations NO 10/2011, and provides a quick and convenient method for the detection of the actual sample.
Description
Technical field
The invention belongs to compound test field, relate to the detection method of harmful 18 kinds of phenols and derivant Special migration thereof in food contact material, particularly relate to a kind of detection method using using high performance liquid chromatography tandem mass spectrum (HPLC-MS/MS) method to measure 18 kinds of phenols and derivant Special migration thereof in Plastic packaging material for food and container.
Technical background
Multiple phenols or phenol derivatives are used as the function additive such as raw material or antioxidant, ultraviolet absorber, biocide mildewcide, molecular weight regulator, add in plastics, to increase performance and the outward appearance of plastic products.But the phenols that part is added or phenol derivatives also have larger toxicity, and the phenols added in some Plastic food contact material goods or phenol derivatives function additive, in use also can move in food, directly be detrimental to health.(EU) NO 10/2011 regulation that European Union issued in 2011, is limited the Special migration of multiple phenols or phenol derivatives.In recent years, the phenols of tool toxic and side effect or also happening occasionally of phenol derivatives is detected in Plastic food contact material correlated product.
At present, both at home and abroad about the detection method detecting limited phenols or phenol derivatives in Plastic food contact material goods mainly contains: vapor-phase chromatography (GC), high performance liquid chromatography (HPLC) and high performance liquid chromatography-tandem mass method (HPLC-MS/MS).And the sum that these detection methods existing also also exist detection phenols or phenol derivatives is simultaneously less, and for the detection of phenols or phenol derivatives in fatty food simulants, mostly do not use the vegetable oil food simulants of (EU) NO 10/2011 rules and regulations, and be the use of the deficiency of the aspects such as isooctane.
Summary of the invention
In order to solve the difficult problem that in Plastic packaging material for food and container, multiple harmful antioxidant Special migration detects simultaneously, improve detection efficiency, the invention provides the detection method that a kind of using high performance liquid chromatography tandem mass spectrum (HPLC-MS/MS) method detects the Special migration of 18 kinds of phenols and derivant thereof in Plastic food contact material, the method has sensitive, accurate, quick, easy feature.
Using high performance liquid chromatography tandem mass spectrum of the present invention (HPLC-MS/MS) method detects the method for the Special migration of 18 kinds of phenols and derivant thereof in Plastic food contact material, is realized by following steps:
One, migration test
According to the practical use of Food Contact plastic products, be injected in testing sample plastic products or glassware according to certain surface-to-volume than by food simulants, after vessel mouth or vessel port seal with surface plate or aluminium-foil paper, in baking oven or incubator, determine that migration temperature and transit time carry out migration test by European Union's NO10/2011 rules and regulations, after be cooled to room temperature, food simulants is wherein transferred in clean glassware and treats subsequent treatment; Wherein food simulants is respectively food simulants A, B, C, D1, D2.
Food simulants is wherein according to European Union (EU) NO 10/2011 rules and regulations, and food simulants A:10% ethanol water (v/v), for simulating the aqueous food of pH > 4.5; Food simulants B:3% acetic acid aqueous solution (w/v), for simulating the acid food of pH < 4.5; Food simulants C:20% ethanol water (v/v), for simulate spirituosity and alcohol content be no more than 20% food; Food simulants D1:50% ethanol water (v/v), for simulating spirituosity and the alcohol content food and the oil-water emulsion that are greater than 20%; Food simulants D2: vegetable oil, for simulating the food of surface containing free-fat.
By European Union (EU) NO 10/2011 rules and regulations, select suitable migration test condition by table 1 Suo Shi according to product practical use.
Table 1 moves the selection of experiment condition
According to European Union (EU) NO 10/2011 rules and regulations, surface-to-volume compares: for < 500mL, > 10L container class plastic products or can not the flat articles of splendid attire, plastic products are sheared and puts into clean glassware, with the ratio of the corresponding 1L food simulants of the surface area of 6dm2 food contact surface; For the container class plastic products of > 500mL, < 10L, then food simulants is injected into apart from container edge 4/5 place.
Two, the process of food simulants
(1) process of food simulants A, B, C, D1: after fully being mixed by each food simulants, draws each food simulants 1 ~ 2mL after above-mentioned dilution with syringe, is filtered in sample injection bottle through hydrophilic polyfluortetraethylemicroporous syringe filters, to be measured;
(2) process of food simulants D2: take vegetable oil food simulants 10g (being accurate to 0.1g) in 50mL tool plug glass centrifuge tube, add 10mL normal heptane and 1mL tetrahydrofuran respectively, after mixing, add 5mL acetonitrile again, screw stopper, be placed in 300r/min on separating funnel oscillator and shake 20min, leave standstill 15min again, upper strata acetonitrile solution 1 ~ 2mL is drawn with 2mL syringe, cross 0.45 μm of teflon syringe filters in sample injection bottle, cover tightly lid, after mixing, to be measured;
Three, blank test
According to food simulants A, B, C, D1, D2 that (1), (2) method process in step 2 do not contact with testing sample.
Four, using high performance liquid chromatography tandem mass spectrum (HPLC-MS/MS) method measures.
Instrument condition:
1) chromatographic column: C8 post, height × internal diameter × thickness=250mm × 4.6mm × 5 μm, or suitable person;
2) mobile phase A: pure water; Mobile phase B: volume fraction is the isopropyl alcohol methanol solution of 25%; Condition of gradient elution: 0 ~ 5.0min:35 ~ 90%B; 5.0 ~ 10.0min:90%B; 10.0 ~ 10.1min:90 ~ 100%B; 10.1 ~ 13.5min:100%B; 13.5 ~ 14.0min:100 – 35%B; 14.0 – 16.5min:35%B;
3) column temperature: 40 DEG C;
4) sample size: 10 μ L;
5) flow velocity before post: 1mL/min;
6) after post, mobile phase introduced by three-way pipe: 0.5% diethylamine aqueous solution;
7) flow rate of mobile phase is introduced after post: 0.20mL/min;
8) electric spray ion source mode of operation: negative ion;
9) data acquisition scheme: multiple-reaction monitoring;
10) curtain gas: 40 μ L/min;
11) gas is collided: medium;
12) electric spray ion source voltage :-4500V;
13) temperature: 700 DEG C;
14) ion source gas: gas 1,70.0 μ L/min; Gas 2,70.0 μ L/min;
15) entrance potential :-10.0V;
16) collision cell exit potential :-8.0V;
17) quantitative manner: calibration curve external standard method, obtains 18 kinds of phenols and derivant Special migration thereof.
The present invention is owing to have employed above-mentioned technical scheme, food simulants A, B, C, D1 water wettability polytetrafluoro acetic acid syringe filters is filtered, food simulants D2 adopts acetonitrile normal heptane liquid liquid to distribute and removes glyceride in vegetable oil, can efficient, easy, measure 18 kinds of phenols and derivant Special migration thereof in Plastic packaging material for food and container fast.According to European Union NO 10/2011 rules and regulations, testing result judges whether Special migration meets the requirements.18 kinds of phenols or phenol derivatives 0.0014 ~ 0.5 times of European Union (EU) NO 10/2011 regulation that is quantitatively limited in five kinds of food simulants is limited the quantity; At 0.25 or 0.5 ~ 5 times of good (r of regulation limitation scope internal linear relation
2>0.9904); 0.5, the recovery of standard addition of 1.5,4.0 times of regulation limitation levels is 74.7% ~ 129%, and relative standard deviation is 0.44% ~ 11.6%.Experimental result shows: the method chromatographic resolution and linear relationship better, the recovery and accuracy high, meet the limitation requirement of 18 kinds of phenols or phenol derivatives Special migration in European Union (EU) NO 10/2011 regulation subordinate list 1, the detection for actual sample provides method quickly and easily.
The invention provides the high performance liquid chromatography-tandem mass method for combined use of 18 kinds of phenols or phenol derivatives Special migration in a kind of Simultaneously test plastic products five kinds of food simulants.Food simulants soaks testing sample, is cooled to room temperature and mixes, and water-based dip liquid is sample introduction after polytetrafluoro acetic acid syringe filters is filtered; After vegetable oil food simulants extracts with acetonitrile, sample introduction after supernatant filters by polytetrafluoro acetic acid syringe filters.Use C
8post gradient elution is separated; Mass spectrum tool electric spray ion source, runs under negative ion multiple-reaction monitoring pattern.The method chromatographic resolution and linear relationship are better, the recovery and accuracy high, meet the limitation requirement of 18 kinds of phenols or phenol derivatives in European Union NO 10/2011 regulation, the detection for actual sample provides method quickly and easily.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail.
Embodiment 1
Using high performance liquid chromatography tandem mass spectrum of the present invention (HPLC-MS/MS) method measures the detection method of 18 kinds of phenols and derivant Special migration thereof in Plastic packaging material for food and container, provides following steps to realize:
One, sample-pretreating method
1, migration test
1.1 food simulants: according to European Union (EU) NO 10/2011 rules and regulations, food simulants A:10% ethanol water (v/v), for simulating the aqueous food of pH > 4.5; Food simulants B:3% acetic acid aqueous solution (w/v), for simulating the acid food of pH < 4.5; Food simulants C:20% ethanol water (v/v), for simulate spirituosity and alcohol content be no more than 20% food; Food simulants D1:50% ethanol water (v/v), for simulating spirituosity and the alcohol content food and the oil-water emulsion that are greater than 20%; Food simulants D2: vegetable oil, for simulating the food of surface containing free-fat.
1.2 transition conditions: according to European Union (EU) NO 10/2011 rules and regulations, select suitable migration test condition by table 2 Suo Shi according to product practical use:
Table 2 moves the selection of experiment condition
1.3 surface-to-volume ratios: according to European Union (EU) NO 10/2011 rules and regulations, for < 500mL, > 10L container class plastic products or can not the flat articles of splendid attire, plastic products are sheared and puts into clean glassware, with the ratio of the corresponding 1L food simulants of the surface area of 6dm2 food contact surface; For the container class plastic products of > 500mL, < 10L, then food simulants is injected into apart from container edge 4/5 place.
1.4 migrations: according to the practical use of Food Contact plastic products, be injected in testing sample plastic products or glassware according to surface-to-volume than by the food simulants selected, after vessel mouth or vessel port seal with surface plate or aluminium-foil paper, migration test is carried out by transition condition setting migration temperature and time in baking oven or incubator, after be cooled to room temperature, food simulants is wherein transferred in clean glassware and treats subsequent treatment.
2, the process of food simulants
The process of 2.1 food simulants A, B, C, D1: after fully being mixed by each food simulants, draws each food simulants 1 ~ 2mL after above-mentioned dilution with syringe, is filtered in sample injection bottle through hydrophilic polyfluortetraethylemicroporous syringe filters, to be measured;
The process of 2.2 food simulants D2: take vegetable oil food simulants 10g (being accurate to 0.1g) in 50mL tool plug glass centrifuge tube, add 10mL normal heptane and 1mL tetrahydrofuran respectively, after mixing, add 5mL acetonitrile again, screw stopper, be placed in 300r/min on separating funnel oscillator and shake 20min, leave standstill 15min again, upper strata acetonitrile solution 1 ~ 2mL is drawn with 2mL syringe, cross 0.45 μm of teflon syringe filters in sample injection bottle, cover tightly lid, after mixing, loading.
3, blank test
The five kinds of food simulants do not contacted with testing sample according to 2.1,2.2 method process in step 2.
Two, Liquid Chromatography-Tandem Mass Spectrometry (HPLC-MS/MS) method condition determination:
Liquid phase chromatogram condition and part Mass Spectrometry Conditions parameter in table 3, the retention time of 18 kinds of phenols and derivant thereof and the parent ion under multiple-reaction monitoring pattern, daughter ion, impact energy and go bunch voltage parameter in table 4.
Table 3 liquid phase chromatogram condition and part Mass Spectrometry Conditions
Table 4 18 kinds of phenols and the parent ion of derivant under multiple-reaction monitoring pattern, daughter ion, impact energy and remove a bunch voltage
Note: "-" expression fails to obtain.
Three, linear relationship and mensuration lower bound, the mensuration lower bound of this method is in table 5:
The mensuration lower bound (unit: μ g/kg) of table 5 method
Get 18 kinds of phenols and the derivant mixed standard solution (see table 6) thereof of variable concentrations, or according to 2.2 operation, and add a series of mixed standard solution (see table 8), and process according to the operation of 2.2, again standard solution or working solution are pressed the determined instrument condition of this method from low concentration to the order of high concentration difference sample introduction successively, with various antioxidant chromatographic peak area, linear regression is done to concentration, its concentration and chromatographic peak area linear relationship good, related coefficient is all greater than 0.9904, the results are shown in Table 7.
The standard solution series concentration (unit: μ g/mL) of table 6 food simulants A, B, C, D1
Table 7 18 kinds of phenols and the range of linearity of derivant in 5 kinds of food simulants, related coefficient, linear equation
Four, the recovery and precision test
Add 18 kinds of phenols and the derivant mixed standard solution thereof of three variable concentrations levels in negative sample respectively, the average recovery of standard addition of six revision tests and precision data are in table 8.
Average recovery of standard addition in five kinds of food simulants of table 8 18 kinds of phenols and derivant thereof and precision (n=6).
The present invention establishes using high performance liquid chromatography tandem mass spectrum coupling (HPLC-MS/MS) method method and detects five kinds of food simulants 10% ethanol, 3% acetic acid, 20% ethanol, 50% ethanol, the method for 18 kinds of specific phenols and derivant Special migration thereof in vegetable oil that contact with Plastic packaging material for food.The method has chromatographic resolution and linear relationship is better, the recovery and accuracy higher, quantitative limit meets the limitation requirement of 18 kinds of phenols and derivant Special migration thereof in European Union (EU) NO10/2011 regulation subordinate list 1, has good using value and prospect.
Claims (3)
1. HPLC/MS-MS 18 kinds of phenols and derivant specific transfer metering method thereof, wherein 18 kinds of phenols and derivant thereof come from Plastic packaging material for food and container, it is characterized in that the method comprises the following steps:
One, migration test
According to the practical use of Food Contact plastic products, be injected in plastic products or glassware according to certain surface-to-volume than by food simulants, after vessel mouth or vessel port seal with surface plate or aluminium-foil paper, in baking oven or incubator, determine that migration temperature and transit time carry out migration test by European Union NO 10/2011 rules and regulations, after be cooled to room temperature, food simulants is wherein transferred in clean glassware and treats subsequent treatment;
Two, the process of food simulants
(1), the process of food simulants A, B, C, D1: after each test solution is fully mixed, draw each food simulants 1 ~ 2 mL after above-mentioned dilution with syringe, be filtered in sample injection bottle through hydrophilic polyfluortetraethylemicroporous syringe filters, to be measured;
(2), the process of food simulants D2: be accurate to 0.1 g and take vegetable oil food simulants 10 g in 50 mL tool plug glass centrifuge tubes, add 10 mL normal heptanes and 1 mL tetrahydrofuran respectively, after mixing, add 5 mL acetonitriles again, screw stopper, be placed in 300 r/min on separating funnel oscillator and shake 20 min, leave standstill 15 min again, upper strata acetonitrile solution 1 ~ 2 mL is drawn with 2 mL syringes, cross 0.45 μm of teflon syringe filters in sample injection bottle, cover tightly lid, after mixing, loading;
Three, blank test
According to the food simulants that (1), (2) method process in step 2 do not contact with testing sample;
Four, liquid chromatography tandem mass spectrometry measures
Instrument condition:
1) chromatographic column: C8 post, height × internal diameter × mm × 5 μm, mm × 4.6, thickness=250, or suitable person;
2) mobile phase A: pure water; Mobile phase B: volume fraction is the isopropyl alcohol methanol solution of 25%; Condition of gradient elution: 0 ~ 5.0 min:35 ~ 90% B; 5.0 ~ 10.0 min:90% B; 10.0 ~ 10.1 min:90 ~ 100% B; 10.1 ~ 13.5 min:100% B; 13.5 ~ 14.0 min:100 – 35% B; 14.0 – 16.5 min:35%B;
3) column temperature: 40 DEG C;
4) sample size: 10 μ L;
5) flow velocity before post: 1 mL/min;
6) after post, mobile phase introduced by three-way pipe: 0.5% diethylamine aqueous solution;
7) flow rate of mobile phase is introduced after post: 0.20 mL/min;
8) electric spray ion source mode of operation: negative ion;
9) data acquisition scheme: multiple-reaction monitoring;
10) curtain gas: 40 μ L/min;
11) gas is collided: medium;
12) electric spray ion source voltage :-4500 V;
13) temperature: 700 DEG C;
14) ion source gas: gas 1,70.0 μ L/min; Gas 2,70.0 μ L/min;
15) entrance potential :-10.0 V;
16) collision cell exit potential :-8.0 V;
17) quantitative manner: calibration curve external standard method.
2. HPLC/MS-MS according to claim 1 18 kinds of phenols and derivant specific transfer metering method thereof, it is characterized in that wherein 18 kinds of phenols and derivant thereof are respectively: 2, 6-xylenol, 4-cumyl phenol, 2, 6-di-t-butyl-4-ethyl-phenol, p-t-butyl phenol, 2, 6-BHT, 1, 1, 1-tri-(4-hydroxy phenyl) ethane, 2, 4-dimethyl-6-(1-methyl pentadecyl) phenol, 1, 2-benzenediol, 1, 3-benzenediol, 1, 4-benzenediol, 4, 4'-dihydroxy biphenyl, 4, 4'-thiobis (the 6-tert-butyl group-3-methylphenol), 2-(4, 6-diphenyl-1, 3, 5-triazine-2-base)-5-hexyl oxygen base-phenol, eugenol, gaultherolin, 2, 3, 6-pseudocuminol, bisphenol S, antiphen.
3. HPLC/MS-MS according to claim 1 18 kinds of phenols and derivant specific transfer metering method thereof, it is characterized in that the food simulants described in migration experiment and surface-to-volume ratio are according to European Union NO 10/2011 rules and regulations, food simulants is respectively: 10% ethanol, 3% acetic acid, 20% ethanol, 50% ethanol, vegetable oil.
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| CN105548395A (en) * | 2015-12-21 | 2016-05-04 | 双钱集团（江苏）轮胎有限公司 | Method for explicit testing of resorcinol in rubber compound formula by liquid chromatogram |
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| CN108107136A (en) * | 2017-12-14 | 2018-06-01 | 四川北方红光特种化工有限公司 | A kind of method of pseudocuminol content in high performance liquid chromatography detection 2,5- xylenols |
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| CN110568104A (en) * | 2019-09-24 | 2019-12-13 | 杭州市质量技术监督检测院 | Method for simultaneously measuring migration volumes of various chlorinated phenols in wooden tableware |
| CN113219077A (en) * | 2021-03-25 | 2021-08-06 | 广东产品质量监督检验研究院（国家质量技术监督局广州电气安全检验所、广东省试验认证研究院、华安实验室） | Method for detecting residual quantity of chlorophenol persistent organic pollutants in animal and vegetable oil |
| CN113418829A (en) * | 2021-06-01 | 2021-09-21 | 厦门市产品质量监督检验院 | Method for detecting migration volume of 4, 4' -biphenol |
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Application publication date: 20151104 |