CN104198640B - In food contact material, aldehydes matter migrates to the assay method of oiliness analogies - Google Patents

In food contact material, aldehydes matter migrates to the assay method of oiliness analogies Download PDF

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CN104198640B
CN104198640B CN201410457878.8A CN201410457878A CN104198640B CN 104198640 B CN104198640 B CN 104198640B CN 201410457878 A CN201410457878 A CN 201410457878A CN 104198640 B CN104198640 B CN 104198640B
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aldehydes matter
analogies
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liquid
contact material
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CN104198640A (en
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曹国洲
朱晓艳
孙萍
刘在美
肖道清
陈少鸿
吴倩
刘江
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Ningbo Institute of Inspection and Quarantine Science Technology
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Abstract

In a kind of food contact material, aldehydes matter migrates to the assay method of oiliness analogies, assay method is as follows: adding mass ratio in reaction vessel is the organic ion liquid of 1:0.75��30 and Oleum Helianthi sample to be extracted, vortex oscillation extracts 1��9min, then ultrasonic extraction 15��20min at 20��70 DEG C, then centrifugal treating 10��20min when 4000��5000rpm again, take off the sub-liquid phase of leafing, utilize high performance liquid chromatography-fluorescence to analyze the content of ionic liquid middle aldehydes matter mutually. Select organic ion liquid as extractant, organic ion liquid is a kind of environmentally friendly organic solvent, there is non-volatile, colourless, odorless feature, use safety and effect of extracting good, extraction results is analyzed by application fluoroscopic examination simultaneously, not only sensitivity well also has higher selectivity, the qualitative of chromatograph and quantitatively on more accurate, improve the accuracy of experimental result.

Description

In food contact material, aldehydes matter migrates to the assay method of oiliness analogies
Technical field
The present invention relates to aldehydes matter detection field, particularly relate to aldehydes matter in a kind of food contact material and migrate to the assay method of oiliness analogies
Background technology
Phenolic compound is the hydroxyl derivant of aromatic hydrocarbons, can be divided into Volatile Phenols and fixedness phenol according to its volatility, is a kind of important industrial chemicals, may be utilized in fabricating dyestuff, medicine, phenolic resin, adhesive etc.Phenolic compound is the chemical toxicant of a kind of moderate strength, can enter internal through mucocutaneous, respiratory tract and digestive tract, low concentration can cause accumulative chronic poisoning, high concentration can cause acute poisoning so that stupor is dead, as skin, mucosa are had strong corrosiveness by phenol, it is possible to suppress central nervous system or infringement Liver and kidney function. It has been reported that phenol liquid pollutes skin area when being 25%, 10 minutes i.e. death, wrongly take and digestive tract can be caused to burn, gastrointestinal perforation occurs, and may occur in which shock, pulmonary edema, liver or renal damage. Some phenolic compounds are also listed in environmental hormone list by EPA, as: bisphenol-A (BPA), animal experiment finds that BPA has oestrogen-like hormone characteristic, the BPA of low dosage can make animal produce the effects such as female sexual precosity, sperm count decline, prostate growth, also there is certain fetal toxicity and teratogenecity simultaneously, can substantially increase the generation of the cancers such as animal ovary cancer, carcinoma of prostate, leukemia.
Food simulants refers to the material of the migration characteristic that simulation real food shows in real-world conditions in contact process with food contact material, can being a kind of solvent or the mixture of several solvent, selecting properly food simulants be the maximum CCP truly assessing food contact material migration problem. Some aldehydes matters in food contact material are moved in food simulants all finite quantity regulations by country variant and area, as the bulletin of MHLW 370 of Japan specifies that in PC material, phenol, bisphenol-A, the p-t-butyl phenol limitation in food simulants is 2.5mg/L; European Union is to the limitation of the p-t-butyl phenol in food simulants specifies it is 0.05mg/L.
Owing to phenolic compound migrates to food simulants in food contact material, concentration is relatively low and matrix composition is complicated, thus in measuring food simulants, during phenolic compound, need to use the extraction of separation and concentration technology such as liquid-liquid extraction, solid phase (micro-) and liquid-liquid-liquid microextraction etc., and above-mentioned several abstraction technique is required for using a certain amount of volatile, organic solvent that toxicity is big, to experimenter and environmentally undesirable. The quantitative approach measuring phenolic compound conventional at present is gas chromatography (GC) and high performance liquid chromatography (HPLC).
Summary of the invention
The technical problem to be solved is to provide aldehydes matter in the food contact material that a kind of Detection results is good and safe to migrate to the assay method of oiliness analogies for prior art.
This invention address that the technical scheme that above-mentioned technical problem adopts is: adding mass ratio in reaction vessel is the organic ion liquid of 1:0.75��30 and Oleum Helianthi sample to be extracted, vortex oscillation extracts 1��9min, then ultrasonic extraction 15��20min at 20��70 DEG C, then centrifugal treating 10��20min when 4000��5000rpm again, take off the sub-liquid phase of leafing, utilize high performance liquid chromatography-fluorescence to analyze the content of ionic liquid middle aldehydes matter mutually.
Above-mentioned Oleum Helianthi sample is the food simulants obtained by migration test by food contact material or the aldehydes matter solution configured by Oleum Helianthi, the mode of migration test has multiple, for instance: phenolic resin-made handle is soaked under 120 DEG C of conditions in Oleum Helianthi the food simulants of 30min.
Phenol, bisphenol-A and p-t-butyl phenol are common aldehydes matter, and therefore the described aldehydes matter in such scheme is the one in phenol, bisphenol-A or p-t-butyl phenol.
Described organic ion liquid is hexafluorophosphate, tetrafluoroborate, chlorination 1-octyl group-3-Methylimidazole., N-EPB, N-butyl pyridinium chloride or the one in chlorination 1-butyl-3-Methylimidazole..
As preferably, described organic ion liquid is tetrafluoroborate.
The preferred mass of described organic ion liquid and Oleum Helianthi sample to be extracted ratio is for 1:30, and the preferred extraction time that described vortex oscillation extracts is 3min, and the preferred extraction temperature of described ultrasonic extraction is 20 DEG C.
The testing conditions of above-mentioned high performance liquid chromatography-fluorescence is:
Liquid-phase condition: leacheate is VAcetonitrile:VWaterThe mixed solution of=30:70, after 17min, linear gradient is changed to VAcetonitrile:VWaterWhen=64:36,19min, acetonitrile changes to 100%, and during 20min, acetonitrile linear change is to 30%, sample size 10 �� L, flow velocity 1mL min-1, post case temperature 40 DEG C;
Chromatographic condition: chromatographic column adopts DiamonsilC18Post, this chromatographic column specification is 150 �� 4.6mm, particle diameter 5 ��m, fluoroscopic examination wavelength: transmitting wavelength is 310nm, and excitation wavelength is 270nm.
Compared with prior art, it is an advantage of the current invention that:
(1) present invention selects organic ion liquid as extractant in Oleum Helianthi sample extraction, compared with volatile, the organic solvent that toxicity is big used in prior art, organic ion liquid is a kind of environmentally friendly organic solvent, there is non-volatile, colourless, odorless feature, use safety and effect of extracting good.
(2) extraction results is analyzed by application fluoroscopic examination, compared with traditional gas chromatography (GC) and high performance liquid chromatography (HPLC), not only sensitivity well also has higher selectivity, the qualitative of chromatograph and quantitatively on more accurate, improve the accuracy of experimental result.
To sum up, the present invention utilizes organic ion liquid as extractant, have studied the kind of organic ion liquid, the treating capacity of aldehydes matter, vortex extraction time and the impact on effect of extracting of the ultrasonic extraction temperature, the detection migrating to oiliness analogies for studying aldehydes matter in food contact material further provides basis.
Accompanying drawing explanation
Fig. 1 is the effect of extracting comparison diagram of different organic ion liquid in the embodiment of the present invention 1;
Fig. 2 is the effect of extracting comparison diagram of different organic ion volumes in the embodiment of the present invention 1;
Fig. 3 is the effect of extracting figure of different vortex extraction times in the embodiment of the present invention 1;
Fig. 4 is the reference colour spectrogram in the embodiment of the present invention 2 under optimum extraction condition;
Fig. 5 is the canonical plotting in the embodiment of the present invention 2 under optimum extraction condition.
Detailed description of the invention
Below in conjunction with accompanying drawing embodiment, the present invention is described in further detail.
Embodiment 1:
1, assay method
Sample treatment: add organic ion liquid and the Oleum Helianthi sample of certain mass ratio in plastic centrifuge tube, vortex oscillation extracts, then ultrasonic extraction is carried out at a certain temperature, then centrifugal treating 10��20min when 4000��5000rpm again, take off the sub-liquid phase of leafing, in the present embodiment, Oleum Helianthi sample is the aldehydes matter solution configured by sunflower oil, and the aldehydes matter in the present embodiment is any one in phenol, bisphenol-A or p-t-butyl phenol.
Testing conditions: utilizing high performance liquid chromatography-fluorescence to analyze the content of aldehydes matter in ionic liquid, instrument is Waters2695e, 2475 fluorescence detectors. Liquid-phase condition: leacheate is VAcetonitrile:VWaterThe mixed solution of=30:70, after 17min, linear gradient is changed to VAcetonitrile:VWaterWhen=64:36,19min, acetonitrile changes to 100%, and during 20min, acetonitrile linear change is to 30%, sample size 10 �� L, flow velocity 1mL min-1, post case temperature 40 DEG C;Chromatographic condition: chromatographic column adopts DiamonsilC18Post, this chromatographic column specification is 150 �� 4.6mm, particle diameter 5 ��m, fluoroscopic examination wavelength: transmitting wavelength is 310nm, and excitation wavelength is 270nm.
2, optimization
2.1, the kind of the organic ion liquid impact on effect of extracting
According to above-mentioned assay method and when same measured, respectively hexafluorophosphate, tetrafluoroborate, chlorination 1-octyl group-3-Methylimidazole., N-EPB, N-butyl pyridinium chloride, chlorination 1-butyl-3-Methylimidazole. are used for the aldehydes matter in Oleum Helianthi sample and extract. Test display chlorination 1-octyl group-3-Methylimidazole., N-EPB, N-butyl pyridinium chloride, chlorination 1-butyl-3-Methylimidazole. effect of extracting are poor, and the effect of extracting of hexafluorophosphate and tetrafluoroborate is better. Compare six kinds of ionic liquids of hexafluorophosphate, tetrafluoroborate class further, i.e. 1-butyl-3-methyl hexafluorophosphate ([C4mim][PF6]), 1-hexyl-3-methyl hexafluorophosphate ([C6mim][PF6]), 1-octyl group-3-methyl hexafluorophosphate ([C8mim][PF6]), 1-butyl-3-methyl tetrafluoroborate ([C4mim][BF4]), 1-hexyl-3-methyl tetrafluoroborate ([C6mim][BF4]), 1-octyl group-3-methyl tetrafluoroborate ([C8mim][BF4]) to the extraction results of aldehydes matter in Oleum Helianthi sample, as shown in Figure 1, [C6mim][BF4] effect of extracting is best.
2.2, the treating capacity of the aldehydes matter impact on effect of extracting
According to above-mentioned assay method and when same measured, take [the C of 0.5mL, 1.0mL, 2.0mL, 2.5mL, 5.0mL, 7.5mL, 10mL, 15mL, 20mL respectively6mim][BF4] as extractant, respectively to the phenol containing certain mass, bisphenol-A, p-t-butyl phenol Oleum Helianthi sample carry out extraction test, make Solvent quantity and be extracted Oleum Helianthi sample quality than respectively 1:0.75,1:1,1:1.5,1:2,1:3,1:6,1:7.5,1:15,1:30. Result is as shown in Figure 2, ionic liquid is different to the extracting power of different phenol, for p-t-butyl phenol, when sample quality is 10g, its extraction has been reached saturated by ionic liquid, phenol is then have the trend reaching balance when sample size reaches 15g, and ionic liquid is then stronger to the extracting power of bisphenol-A, also shows stronger extracting power when sample size reaches 20g.
Due to [C6mim][BF4] extraction of p-t-butyl phenol is substantially reached balance when 7.5g, and when sample size is 10g, the detection limit of sample can meet the limitation requirement of European Union bisphenol-A limitation 0.6mg/kg and p-t-butyl phenol 0.05mg/kg, and in practical operation, vortex is produced relatively difficult when sample size is 20g, therefore the present embodiment selects the sample quality extracted to be 15g, and namely ionic liquid consumption and sample quality ratio is for 1:30.
2.3, the vortex time impact on effect of extracting
According to above-mentioned assay method and when same measured, investigating vortex extraction time respectively is effect of extracting when 0min, 1min, 2min, 3min, 5min, 7min, 9min, result is as shown in Figure 3, extract namely up to balance after vortex oscillation 1min, it is contemplated that time slightly longer extraction efficiency is more easy to and reaches unanimity, so the present embodiment selects vortex time to be 3min.
2.4, the ultrasonic temperature impact on effect of extracting
According to above-mentioned assay method and when same measured, during research ultrasonic extraction, extraction temperature is effect of extracting when 20 DEG C, 30 DEG C, 40 DEG C, 50 DEG C, 60 DEG C, 70 DEG C respectively, found that temperature is on extracting almost without impact, but extraction temperature height easily causes ionic liquid dissolubility in Oleum Helianthi to improve, more than 40 DEG C just have been observed that the material having one layer of emulsion layer class between ionic liquid and Oleum Helianthi, being unfavorable for the separation and Extraction of ionic liquid, therefore the temperature of selected ultrasonic extraction is 20 DEG C.
Can being obtained from above, optimum extraction condition is: organic ion liquid selects the mass ratio of tetrafluoroborate, organic ion volume and aldehydes matter to be extracted to be 1:30, and vortex oscillation extraction time is 3min, and ultrasonic extraction temperature is 20 DEG C.
2.5, optimum extraction condition compares with existing extracting process
Migration test: phenolic resin-made handle soaks 30min in Oleum Helianthi and obtains sunflower oil analogies under 120 DEG C of conditions.
At present for the bisphenol-A in oiliness analogies, the method for EN13130-13-2005 is with methanol: water (1:1) extracts. Three kinds of aldehydes matters are extracted by method described in application EN13130-13-2005, and compare with the scheme of the present embodiment, it has been found that organic ion liquid extraction phenol that the present embodiment adopts, bisphenol-A, p-t-butyl phenol bioaccumulation efficiency be the 10 of EN method, 10 and 18 times respectively.
Extracting by method Pyrogentisinic Acid's positive of EN, extract fluoroscopic examination also compares with the method for the present embodiment, and result is as shown in table 1, it is seen that the effect of extracting of the optimum extraction condition of the present embodiment is more preferably.
Table 1
Embodiment 2: the mensuration of linear equation, detection limit and reference colour spectrogram
The configuration of phenols standard sample: weigh 7 parts of ionic liquid 0.5745g respectively and be separately added in 7 test tubes, then in 7 test tubes, add 0.0200g respectively, 0.15g, 0.6g, 1.2g, 5.0g, 15.0g the aldehydes matter mark liquid that concentration is 10mg/kg and the aldehydes matter mark liquid that 15.00g concentration is 20mg/kg, and in each pipe, add Oleum Helianthi respectively, making the sample size in every pipe is 15.00g, the now concentration respectively 0.0133mg/kg of aldehydes matter in each pipe, 0.10mg/kg, 0.40mg/kg, 0.8mg/kg, 3.33mg/kg, 10.0mg/kg, 20.0mg/kg.
Adopt the optimum extraction condition obtained in embodiment 1 that above-mentioned phenols standard sample is extracted, after extraction, carry out upper machine analysis. The range of linearity of phenol, bisphenol-A and p-t-butyl phenol, repeatability (relative standard deviation) and detection limit (S/N=3) are as shown in table 2, in the concentration range measured, the peak area value (y) that the concentration (x) of phenol, bisphenol-A and p-t-butyl phenol is corresponding presents good linear relationship, the RSD (relative standard deviation) < 2% of 3 kinds of materials, has good repeatability; Fig. 4 is reference colour spectrogram, and Fig. 5 is canonical plotting, and relative standard deviation is through pre-treatment by the aldehydes matter mark-on sample that concentration is 1mg/kg, and upper machine calculates and obtains.
Table 2
Embodiment 3: determination of recovery rates
Under above-mentioned optimum extraction condition, utilize additive process to measure the response rate of this assay method. Adopt additive process, above-mentioned gained sunflower oil analogies are added phenol, bisphenol-A and p-t-butyl phenol respectively, interpolation concentration respectively 1.0mg/kg, 2.0mg/kg and 4.0mg/kg of every kind of aldehydes matter, each interpolation concentration level measures 6 times, carrying out response rate calculating, recovery test result is as shown in table 3. From table 3, the response rate of this assay method is good, and this assay method is to the response rate of phenol, bisphenol-A and p-t-butyl phenol in sunflower oil analogies respectively 93.8 �� 1.7%��103.9 �� 1.4%, 88.0 �� 1.9%��97.0 �� 1.7%, 97.0 �� 3.5%��104.0 �� 2.5%.
Table 3

Claims (5)

1. in a food contact material, aldehydes matter migrates to the assay method of oiliness analogies, it is characterized in that: adding mass ratio in reaction vessel is the organic ion liquid of 1:0.75��30 and Oleum Helianthi sample to be extracted, vortex oscillation extracts 1��9min, then ultrasonic extraction 15��20min at 20��70 DEG C, then centrifugal treating 10��20min when 4000��5000rpm again, take off the sub-liquid phase of leafing, high performance liquid chromatography-fluorescence is utilized to analyze the content of ionic liquid middle aldehydes matter mutually, described aldehydes matter is phenol, one in bisphenol-A or p-t-butyl phenol, described organic ion liquid is the one in hexafluorophosphate or tetrafluoroborate.
2. in food contact material as claimed in claim 1, aldehydes matter migrates to the assay method of oiliness analogies, it is characterised in that: described Oleum Helianthi sample is the Oleum Helianthi analogies obtained by migration test by food contact material or the aldehydes matter solution configured by Oleum Helianthi.
3. in food contact material as claimed in claim 1, aldehydes matter migrates to the assay method of oiliness analogies, it is characterised in that: described organic ion liquid is tetrafluoroborate.
4. in food contact material as claimed in claim 1, aldehydes matter migrates to the assay method of oiliness analogies, it is characterized in that: the mass ratio of described organic ion liquid and Oleum Helianthi sample to be extracted is 1:30, described vortex oscillation extraction time is 3min, and described ultrasonic extraction temperature is 20 DEG C.
5. in food contact material as claimed in claim 1, aldehydes matter migrates to the assay method of oiliness analogies, it is characterised in that: in described high performance liquid chromatography-fluorescence,
Liquid-phase condition: leacheate is VAcetonitrile:VWaterThe mixed solution of=30:70, after 17min, linear gradient is changed to VAcetonitrile:VWaterWhen=64:36,19min, acetonitrile changes to 100%, and during 20min, acetonitrile linear change is to 30%, sample size 10 �� L, flow velocity 1mL min-1, post case temperature 40 DEG C;
Chromatographic condition: chromatographic column adopts DiamonsilC18Post, this chromatographic column specification is 150 �� 4.6mm, particle diameter 5 ��m, fluoroscopic examination wavelength: transmitting wavelength is 310nm, and excitation wavelength is 270nm.
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