CN111198242B - Method for determining bisphenol compounds in food simulants - Google Patents
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Abstract
The invention relates to a method for determining bisphenol compounds in a food simulant, which comprises the following steps: precisely weighing bisphenol compounds, dissolving the bisphenol compounds in an organic solvent to obtain a standard solution; preparation of a solution to be tested: accurately measuring a food simulant after the food packaging material migrates the sample, and taking the food simulant as a solution to be measured; and (3) detection: and respectively injecting the standard solution and the solution to be detected into a high performance liquid chromatography-tandem mass spectrometer for detection. On the platform constructed by the scheme, one or more bisphenol compounds in the 14 bisphenol compounds contained in the food simulant can be detected, and the method is also suitable for one or more food simulants, so that the complicated operation that in the traditional technology, detection schemes need to be given for different phenol compounds contained in specific types of food simulants due to the fact that the structure and property differences of the bisphenol compounds are large is avoided, and the method has the advantages of wide detection range and strong applicability. And is accurate, reliable, fast and sensitive.
Description
Technical Field
The invention relates to the technical field of quality detection of food contact materials, in particular to a method for determining bisphenol compounds in a food simulant.
Background
Bisphenols are compounds in which two hydroxyphenyl groups are linked by one or more carbon atoms, or by other atoms such as a sulfur atom and an oxygen atom. The molecular structural formula of the bisphenol compound is shown as the following formula 1, wherein, the intermediate connecting part R can have various structures and can be one or more carbon atoms, such as-CH 2 -、-CH(CH 3 )-、-CH 2 (CH 2 ) n-and the like, and may also be a sulfur atom, such as-SO 2 Other more complex structures are also possible. R 1 And R 2 Moieties may be hydrogen, halogen, alkyl, alkoxy, carboxyl, aromatic groups, and the like.
Bisphenol compounds are an important chemical product. Phenolic hydroxyl in the bisphenol compound has reactivity, can be used as a raw material or a stabilizer, an accelerator, a modifier, a photoinitiator, a flame retardant and the like in the synthesis of high polymer materials such as epoxy resin, polycarbonate, phenolic resin, polyurethane and the like, has a certain effect on improving the heat resistance, humidity resistance, insulating performance, optical performance and the like of the materials, has the characteristics of easy dissolution, high refractive index, high transparency and the like, and is widely applied to the fields of packaging materials, coatings, film materials, electronic product manufacturing and the like. Bisphenol compounds are widely applied in the field of food contact materials, wherein currently most used substances are Bisphenol A (Bisphenol A, BPA), Bisphenol F (Bisphenol F, BPF) and Bisphenol S (Bisphenol S, BPS), but the three substances have certain interference effect on human body secretion systems and are highly concerned, and the use of the compounds in the food contact materials is limited or prohibited by regulations and standards in a plurality of countries and regions in the world, wherein specific migration limits of BPA and BPS in the food contact materials and products are respectively 0.6mg/kg and 0.05mg/kg by European Union (EU) No 10/2011 and national standard GB 9685-. In recent years, other bisphenols having similar structures have been studied extensively in the hope of being used as substitutes. However, due to the structural similarity, bisphenol compounds generally have endocrine disrupting effects and can cause adverse effects on human health, so that the development of detection research on the compounds has important significance for monitoring the quality safety of related products.
Food can not avoid directly contacting with food packaging material in the processes of storage, transportation, use and the like, so that harmful substances in the food contacting material can migrate into the food and further enter the human body. In recent years, with the increasing attention of consumers to the quality safety of food packaging materials and the more and more specific requirements of the national standards of food safety on the quality of food contact materials, research on migration and detection of harmful substances in food contact materials into food simulants is emerging.
Although the detection of bisphenol compounds by ultra performance liquid chromatography tandem mass spectrometry has been reported at present, for example: the prior art discloses a method for determining octanol/water distribution coefficients of bisphenol compounds by using an ultra-high performance liquid chromatography tandem mass spectrometer, and the technical scheme discloses that eight bisphenol compounds are determined by using an ultra-high performance liquid chromatography mass spectrometer: BPC, BPS, BPA, TBBPA, BPAF, BPB, TDP and PPDP. However, no report has been found yet for applying the ultra performance liquid chromatography tandem mass spectrometry technology to the migration detection of harmful substances in food contact materials to food simulants.
Therefore, it is urgent to provide a method for detecting bisphenol compounds based on the ultra performance liquid chromatography tandem mass spectrometry technology.
Disclosure of Invention
Based on the above, the main object of the invention is a method for determining bisphenol compounds in a food simulant, in particular to a method for determining bisphenol compounds in a food simulant by UPLC-MS/MS.
The purpose of the invention is realized by the following technical scheme:
a method for UPLC-MS/MS determination of bisphenols in a food simulant, said method comprising:
preparation of standard solution: precisely weighing bisphenol compounds, dissolving the bisphenol compounds in an organic solvent to obtain a standard solution;
preparation of a solution to be tested: accurately measuring a food simulant after the food packaging material migrates the sample, and purifying the food simulant to be used as a solution to be measured;
and (3) detection: respectively injecting the standard solution and the solution to be detected into a high performance liquid chromatography-tandem mass spectrometer for detection;
the bisphenol compound is selected from at least one of BPA, BPF, BPB, BPC, BPS, TBBPA and BPAF, and at least one of BPE, BPG, DMBPA, BPOPPA, BPAP, BPBP and BPP; the food simulant is at least one selected from water, acetic acid solution with the volume percentage of 4%, ethanol solution with the volume percentage of 10%, ethanol solution with the volume percentage of 20%, ethanol solution with the volume percentage of 50%, ethanol solution with the volume percentage of 95% and olive oil.
In some of these embodiments, the bisphenol compound is a combination of BPA, BPF, BPB, BPC, BPS, TBBPA, BPAF, BPE, BPG, DMBPA, BPOPPA, BPAP, BPBP, BPP; the food simulant is selected from seven of water, acetic acid solution with volume percentage of 4%, ethanol solution with volume percentage of 10%, ethanol solution with volume percentage of 20%, ethanol solution with volume percentage of 50%, ethanol solution with volume percentage of 95% and olive oil.
In some of these examples, the methods were performed according to the following conditions:
a chromatographic column: a chromatographic column with the carbon octadecyl ethylene bridge hybrid particles as filler;
mobile phase: taking 0.8mmol/L-1.2mmol/L ammonium acetate solution as a mobile phase A and methanol as a mobile phase B;
elution gradient: 0min-1.5min, 10% B; 1.5min-2min, 10% -30% B; 2min-3min, 30% -55% B; 3min-6min, 55% -65% B; 6min-7min, 65% -70% B; 7min-8min, 70% B; 8-12min, 70-72% B; 12min-13min, 72% -75% B; 13min-14min, 75% -90% B; 14min-14.1min, 90% -10% B; 14.1-16min, 10% B.
In some of these examples, the methods were performed according to the following conditions:
a chromatographic column: waters ACQUITY UPLC BEH C 18 (2.1mm×100mm×1.7μm)；
Mobile phase: taking 1mmol/L ammonium acetate solution as a mobile phase A and methanol as a mobile phase B;
elution gradient: 0-1.5min, 10% B; 1.5-2min, 10% -30% of B; 2-3min, 30% -55% B; 3-6min, 55% -65% B; 6-7min, 65% -70% B; 7-8min, 70% B; 8-12min, 70% -72% B; 12-13min, 72% -75% B; 13-14min, 75% -90% B; 14-14.1min, 90% -10% B; 14.1-16min, 10% B.
In some of these examples, the methods were performed according to the following conditions:
flow rate: 0.2mL/min-0.4 mL/min;
sample introduction amount: 3-7 μ L;
column temperature: 28-32 ℃.
In some of these examples, the methods were performed according to the following conditions:
flow rate: 0.3 mL/min;
sample introduction amount: 5 mu L of the solution;
column temperature: at 30 ℃.
In some of these examples, the method performs mass spectrometry according to the following conditions:
an ion source: an electrospray ion source;
scanning mode: a negative ion mode;
detection mode: monitoring multiple reactions;
spraying voltage: 3400V-3600V;
evaporation temperature: 370-390 ℃;
ion transfer tube temperature: 315-335 ℃;
sheath gas: nitrogen, 35Arb-45 Arb;
auxiliary gas: nitrogen, 3Arb-10 Arb;
collision gas: argon, 1mTorr-3 mTorr.
In some of these examples, the method performs mass spectrometry according to the following conditions:
an ion source: an electrospray ion source;
scanning mode: a negative ion mode;
detection mode: monitoring multiple reactions;
spraying voltage: 3500V;
evaporation temperature: 380 ℃;
ion transfer tube temperature: 325 ℃;
sheath gas: nitrogen, 40 Arb;
auxiliary gas: nitrogen, 5 Arb;
collision gas: argon, 1.5 mTorr.
In some of these examples, the organic solvent is methanol in the preparation of the standard solution.
In some embodiments, the standard solution comprises BPE, BPA, BPB, BPF, TBBPA, BPC, BPG, DMBPA and BPOPPA at a concentration of 1.0 μ g/L to 200.0 μ g/L, BPAP, BPBP and BPP at a concentration of 0.2 μ g/L to 40.0 μ g/L, and BPS and BPAF at a concentration of 0.05 μ g/L to 10.0 μ g/L.
Compared with the prior art, the invention has the following beneficial effects:
the UPLC-MS/MS method provided by the invention, particularly the method formed by matching with proper detection conditions, is a new scheme for detecting bisphenol compounds in food simulants. The scheme successfully constructs a bisphenol compound detection platform with wide detection range and strong applicability. On the platform, one or more bisphenol compounds in BPA, BPF, BPB, BPC, BPS, TBBPA, BPAF, BPE, BPG, DMBPA, BPOPPA, BPAP, BPBP and BPP contained in the food simulacra can be detected, and the platform is also suitable for one or more food simulacra, so that the complicated operation that a specific detection scheme is required to be provided for different bisphenol compounds contained in specific types of food simulacra due to the large difference of structures and properties of the bisphenol compounds in the traditional technology is avoided, and the platform has the advantages of wide detection range and strong applicability. And the detection method is accurate, reliable, rapid and sensitive.
Drawings
FIG. 1 is a Multiple Reaction Monitoring (MRM) chromatogram of 14 bisphenols.
Detailed Description
In order that the invention may be more fully understood, reference will now be made to the following description. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
In the present invention, Bisphenol compounds commonly used in 14 polymer material fields of BPA, BPF, BPS, Bisphenol B (Bisphenol B, BPB), Bisphenol E (Bisphenol E, BPE), Bisphenol AP (Bisphenol AP, BPAP), Bisphenol BP (Bisphenol BP, BPBP), Hexafluorobisphenol a (hexafluorobiphenol a, BPAF), Tetrabromobisphenol a (Tetrabromobisphenol a, TBBPA), Bisphenol C (Bisphenol C, BPS), Bisphenol G (Bisphenol G, BPG), Bisphenol P (Bisphenol P, BPP), 3 '-dimethyl Bisphenol a (, 3' -dimethyl biphenol a, DMBPA), Bisphenol OPPA (bisphenoxypa, BPA) are selected as test objects (structural formula below), and a test for selecting a food contact material and a product migration test requires a test for simulating a volume fraction of water (31604.1% in a test sample of a food material, namely, a test volume fraction of acetic acid (volume fraction) (volume fraction of acetic acid) (894% and acetic acid) (volume fraction of acetic acid, namely, 10% in a test sample of a test object for selecting a food contact material and a product migration test for a product 20 percent (volume fraction) ethanol, 50 percent (volume fraction) ethanol, 95 percent (volume fraction) ethanol and olive oil (vegetable oil) are used as research matrixes, the research matrixes are purified by adopting a solid-phase extraction mode, and the research matrixes are separated and analyzed by adopting ultra performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS). The established method is accurate, reliable, rapid and sensitive, has wide coverage range and strong applicability, and can provide technical support and method reference for detecting and monitoring the migration quantity of the bisphenol compounds in the food contact material.
Example 1
This example provides a method for detecting 14 bisphenols in a food mimetic, comprising the following steps:
1 experimental part
1.1 Main instruments and devices
Thermo TSQ Quantuva ultra high performance liquid chromatography-tandem mass spectrometer (semer flyer usa); high speed refrigerated centrifuge (Allegra) TM 64R, BECKMAN); ultrapure water systems (Milli-Q, Millipore, USA); nitrogen blowing instrument (N-EVAP) TM 111, organization, usa); MS3 type vortex oscillator (IKA MS3, uka germany); analytical balance (BSA224S, sardolis, germany); solid phase extraction apparatus (CNW, germany); oasis HLB solid phase extraction cartridge (200mg, 6mL, Waters corporation, usa).
1.2 Main materials and reagents
Standard or control: BPA, BPF and TBBPA, the purity is more than or equal to 98.5 percent, and the product is produced by Dr. BPB and BPS with purity not less than 98%, products of Accustandard company of America; BPE with purity not less than 98.5%, BPG with purity not less than 98%, Sigma-Aldrich company of America; BPAF, BPAP, BPC, DMBPA, the purity is more than or equal to 98 percent, products of Germany CNW company; BPBP, BPP, BPOPPA, purity all equal to or greater than 98%, Japanese TCI company products; methanol (Mass Spectrometry pure, product of Merck, Germany); acetic acid, n-hexane, acetonitrile and ethanol (chromatographically pure, Spectrum corporation, usa); olive oil (analytical pure, guangzhou chemical reagent factory); the experimental water was deionized water filtered through a Milli-Q purification system.
1.3 Standard solution preparation
Accurately weighing 0.01g (accurate to 0.01mg) of standard substance in a 10mL volumetric flask, preparing 1000mg/L single-standard stock solution by using methanol, accurately transferring a proper amount of each single-standard stock solution in the 10mL volumetric flask, performing constant volume by using methanol to prepare a mixed standard stock solution with BPE, BPA, BPB, BPF, TBBPA, BPC, BPG, DMBPA and BPOPPA concentrations of 20.0mg/L, BPAP, BPBP and BPP concentrations of 4.0mg/L and BPS and BPAF concentrations of 1.0mg/L, and storing at-20 ℃. When in use, the solution is diluted into a series of standard working solutions with concentration by methanol and is prepared for use.
In other embodiments, the concentration of BPE, BPA, BPB, BPF, TBBPA, BPC, BPG, DMBPA, BPOPPA is 1.0-200.0 μ g/L, the concentration of BPAP, BPBP, BPP is 0.2-40.0 μ g/L, and the concentration of BPS, BPAF is 0.05-10.0 μ g/L. The response of different bisphenol compounds is greatly different, and mixed standard solutions with different concentrations are prepared in order to enable the response of each compound to be on the same level.
1.4 sample pretreatment
1.4.1 pretreatment
Migration tests were carried out according to the requirements of GB 31604.1-2015 and GB 5009.156-2016. Taking water as a food simulant as an example: according to the contact area, per 6dm 2 The food packaging material is added with 1L of water or added with water to a position 2mm below the highest position of a container (container type products) for carrying out a migration test.
The different types of food simulants were pre-treated in different ways, as follows:
(1) water, 4% (volume fraction) acetic acid, 10% (volume fraction) ethanol, 20% (volume fraction) ethanol:
the clarified food simulant after the migration test is accurately measured by 10mL without being pretreated, and is subjected to solid phase extraction and purification. And centrifuging a proper amount of the unclarified food simulants after the migration test for 5min at 5000r/min, accurately measuring 10mL of supernate, and performing solid-phase extraction and purification.
(2) 50% (volume fraction) ethanol:
accurately transferring 4mL of ethanol simulant (volume fraction) with 50 percent after the migration test into a colorimetric tube with the diameter of 10m, adding water to fix the volume to 10mL, uniformly mixing, centrifuging at 5000r/min for 5min if necessary, and waiting for solid phase extraction and purification.
(3) 95% (volume fraction) ethanol:
accurately transferring 2mL of ethanol simulant (volume fraction) with 50 percent after the migration test into a colorimetric tube with the diameter of 10m, adding water to fix the volume to 10mL, uniformly mixing, centrifuging at 5000r/min for 5min if necessary, and performing solid phase extraction and purification.
(4) Olive oil:
accurately weighing 1g (accurate to 0.001g) of the olive oil simulant after the migration test in a 10mL colorimetric tube, adding 1mL of n-hexane, fully mixing, adding 2mL of acetonitrile, carrying out vortex oscillation for 2min, centrifuging at 5000r/min for 5min, and taking the upper solution to the 10mL colorimetric tube; adding 2mL of acetonitrile into the lower-layer liquid for repeated extraction once, combining the upper-layer extracting solutions, blowing nitrogen in a water bath at 45 ℃ until the upper-layer extracting solutions are nearly dry, dissolving 10% (volume fraction) of methanol aqueous solution, and fixing the volume to 10mL until solid phase extraction and purification are carried out.
1.4.2 solid phase extraction purification
The HLB solid phase extraction column is activated by 5mL of methanol and 5mL of water in advance in sequence, a food simulant pretreated according to 1.4.1 is sampled, then is rinsed by 5mL of water and 5mL of 10% (volume fraction) acetonitrile aqueous solution in sequence, after blow-drying, is eluted by 10mL of methanol, the volume is determined to be 10mL, and a proper amount of the sample is filtered through a 0.22-micron microporous filter membrane to obtain a solution to be detected.
1.5 test conditions
1.5.1 chromatographic conditions
A chromatographic column: waters ACQUITY UPLC BEH C 18 (2.1mm×100mm×1.7μm)；
Mobile phase: 1mmol/L ammonium acetate solution (A) and methanol (B);
gradient elution procedure: 0-1.5min, 10% B; 1.5-2min, 10% -30% of B; 2-3min, 30% -55% of B; for 3-6min, 55-65% of B; 6-7min, 65-70% of B; 7-8min, 70% B; for 8-12min, 70-72% of B; 12-13min, 72% -75% of B; 13-14min, 75% -90% of B; 14-14.1min, 90% -10% of B; 14.1-16min, 10% B.
Flow rate: 0.3 mL/min;
sample introduction amount: 5 mu L of the solution;
column temperature: at 30 ℃.
1.5.2 Mass Spectrometry conditions
An ion source: electrospray ion source (ESI);
scanning mode: a negative ion mode;
detection mode: multiple Reaction Monitoring (MRM);
spraying voltage: 3500V;
evaporation temperature: 380 ℃;
ion transfer tube temperature: 325 ℃;
sheath gas: nitrogen, 40 Arb;
auxiliary gas: nitrogen, 5 Arb;
collision gas: argon, 1.5 mTorr.
Other mass spectral parameters are shown in table 1.
Table 1, retention time and mass spectrometry parameters for 14 bisphenols
2 results and discussion
2.1 optimization of chromatographic conditions
The polarity of the 14 bisphenols tested in this example was very different (see table 2 for parameters), and the separation was performed by gradient elution. In the experiments:
the mobile phase A examines water, a 1mmol/L ammonium acetate solution and a 0.05% ammonia water solution, and the result shows that 14 bisphenol compounds have good retention effect and peak shape by adopting the water and the 1mmol/L ammonium acetate solution as the mobile phase, but better response can be obtained by adopting the 1mmol/L ammonium acetate solution. When 0.05% ammonia water solution is adopted, the response of compounds with small logP values such as BPS, BPF, BPE and BPA is low, the retention factors of BPS, BPAF and TBBPA are obviously reduced, and the response is reduced, probably because the pKa value of phenolic hydroxyl groups in the 3 bisphenol compounds is low, and the phenolic hydroxyl groups exist in the solution in the form of salt under the alkaline condition, so that the retention effect in a reversed phase chromatographic column is reduced, and the ionization efficiency is also reduced.
Further examining the responses of 14 compounds when ammonium acetate solutions with different concentrations (1-10 mmol/L) are used as the mobile phase, the results show that the responses of 14 compounds are enhanced as the concentration of ammonium acetate is reduced, and the mobile phase A finally selects 1mmol/L ammonium acetate solution.
The optimized chromatogram is shown in FIG. 1, wherein 1 is BPS, 2 is BPF, 3 is BPE, 4 is BPA, 5 is BPB, 6 is BPC, 7 is BPAF, 8 is BPAP, 9 is DMBPA, 10 is BPBP, 11 is TBBPA, 12 is BPG, 13 is BPP, and 14 is BPOPPA.
Table 2, 14 physicochemical parameters of bisphenols
2.2 optimization of the conditions for solid phase extraction
Considering the physicochemical properties of 14 compounds:
contrast and investigate C 18 The column and the HLB column have the purification effect of two general solid-phase extraction small columns. The results show that C is used 18 The recovery rate of BPS is lower than 70% when using the column, while the recovery rate is better when using the HLB column, and the analysis probably is because the logP value of BPS is lower and is C 18 The retention on the column is weaker, while the retention on the HLB column with hydrophilic-lipophilic balance properties is better. The other 13 bisphenols have good effect on both extraction columns, so the HLB column is used as the solid phase extraction cartridge.
The sample loading liquid is examined, and the result shows that when the content of the methanol or the ethanol in the sample loading liquid is lower than 20%, the sample loading is 10mL, 14 bisphenol compounds are not obviously lost, and when the ratio of the methanol to the ethanol is further increased, BPS and BPF are slightly lost.
Meanwhile, the purifying effects of the 10% acetonitrile aqueous solution, the 10% methanol aqueous solution and the 20% methanol aqueous solution as the leacheate on 14 bisphenol compounds in the sample liquid are examined, and the results show that the adding recovery rate of BPS, BPF, BPE, BPA and BPB is less than 40% when the 20% methanol aqueous solution is used for leaching; when the 10% acetonitrile water solution is used for leaching, the addition recovery rate of 14 compounds is more than 75%, but the baseline noise is large at the moment, and the impurity removal effect is not obvious; when the 10% methanol aqueous solution is used for leaching, the addition recovery rate of 14 compounds is more than 78%, and the baseline noise is low, so that the 10% methanol aqueous solution is selected for leaching and purifying the sample solution.
2.3 Linear relationship and detection limits of the method
Preparation of 14 by using methanol as solventA series of mixed standard solutions of bisphenol compounds are prepared, wherein the concentrations of BPE, BPA, BPB, BPF, TBBPA, BPC, BPG, DMBPA and BPOPPA are 1.0-200.0 mug/L, the concentrations of BPAP, BPBP and BPP are 0.2-40.0 mug/L, and the concentrations of BPS and BPAF are 0.05-10.0 mug/L, and the solutions are measured under the chromatographic and mass spectrometric conditions of 1.4. The standard curve is plotted as peak area (Y) and corresponding mass concentration (x). The linear range, linear equation and correlation coefficient of the 14 bisphenols are shown in table 3. The 14 bisphenol compounds have good linear relation and correlation coefficient (R) in respective concentration ranges 2 ) Are all greater than 0.999.
TABLE 3, Linear equation, Linear Range, correlation coefficient of 14 bisphenols
The detection limit (S/N.gtoreq.3) and the quantification limit (S/N.gtoreq.10) for the 14 bisphenols in the different types of food simulants are shown in Table 4.
TABLE 4 detection and quantitation limits (%: by volume) of 14 bisphenols in different types of food simulants
2.4 recovery and precision of the method
The recovery and precision of the method were examined by adding 3 concentration levels (see table 5 and table 5) of standard solutions to 7 food simulants, treating them at 1.4.2, and measuring each concentration in parallel 6 times. The results are shown in Table 5 and Table 5. The result shows that the recovery rate of the three standard adding steps is 78.1-114.8%, the relative standard deviation is 1.3-6.3%, and the result shows that the method has good accuracy and precision and can meet the requirement of measuring the migration quantity of 14 bisphenol compounds.
Table 5 recovery and precision of 14 bisphenols from different types of food simulants (n ═ 6)
Table 5 recovery and precision of 14 bisphenols from different types of food simulants (n ═ 6)
3 conclusion
This example establishes an ultra performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) assay for 14 bisphenols in 7 food mimetics. The method aims at 7 food simulators, completely covers the requirements on migration conditions in national standards, and has wide applicability. The target compound in the olive oil is dispersed by normal hexane and then extracted by acetonitrile, other types of food simulants do not need to be treated or are purified by an HLB solid phase extraction column after the solvent type is properly adjusted, and the UPLC-MS/MS is used for separation and analysis. By optimizing the solid phase extraction purification condition and the chromatographic condition, 14 bisphenol compounds can be effectively separated, the detection limit can reach 0.01-0.2 mu g/kg, and the parameters of the standard addition recovery rate, the precision and the like can meet the requirements of the analysis method. The established method is accurate, reliable, rapid and sensitive, the coverage range of the detection object and the food simulant type is wide, the applicability is strong, and the method can provide technical support and method reference for detecting and monitoring the migration quantity of the bisphenol compounds in the food contact material.
Example 2 practical test application
The method is adopted to detect 100 parts of food contact materials and products, and relates to product types including polycarbonate buckets, feeding bottles, water cups, food metal cans, food metal covers and the like. The detection results show that the BPA migration amount is detected in 14 parts of food metal cover samples, and the BPF migration amount is detected in 1 part of food metal cover samples, and the specific detection results are shown in Table 6.
TABLE 6 positive sample test results (%: vol.)
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that various changes and modifications can be made by those skilled in the art without departing from the spirit of the invention, and these changes and modifications are all within the scope of the invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (8)
1. A method for determining bisphenol compounds in a food simulant by UPLC-MS/MS, the method comprising:
preparation of standard solution: precisely weighing bisphenol compounds, dissolving the bisphenol compounds in an organic solvent to obtain a standard solution;
preparation of a solution to be tested: accurately measuring a food simulant after the food packaging material migrates the sample, and purifying the food simulant to be used as a solution to be measured;
and (3) detection: respectively injecting the standard solution and the solution to be detected into a high performance liquid chromatography-tandem mass spectrometer for detection;
the bisphenol compound is the combination of BPA, BPF, BPB, BPC, BPS, TBBPA, BPAF, BPE, BPG, DMBPA, BPOPPA, BPAP, BPBP and BPP;
the food simulant is selected from seven of water, acetic acid solution with the volume percentage of 4%, ethanol solution with the volume percentage of 10%, ethanol solution with the volume percentage of 20%, ethanol solution with the volume percentage of 50%, ethanol solution with the volume percentage of 95% and olive oil;
the method is used for carrying out high performance liquid chromatography tests according to the following conditions:
a chromatographic column: a chromatographic column with the carbon octadecyl ethylene bridge hybrid particles as filler;
mobile phase: taking 0.8mmol/L-1.2mmol/L ammonium acetate solution as a mobile phase A and methanol as a mobile phase B;
elution gradient: 0min-1.5min, 10% B; 1.5min-2min, 10% -30% B; 2min-3min, 30% -55% B; 3min-6min, 55% -65% B; 6min-7min, 65% -70% B; 7min-8min, 70% B; 8-12min, 70-72% B; 12min-13min, 72% -75% B; 13min-14min, 75% -90% B; 14min-14.1min, 90% -10% B; 14.1-16min, 10% B.
2. The method of claim 1, wherein the method is performed according to the following conditions:
a chromatographic column: waters ACQUITY UPLC BEH C 18 ，2.1 mm×100 mm×1.7 µm；
Mobile phase: taking 1mmol/L ammonium acetate solution as a mobile phase A and methanol as a mobile phase B;
elution gradient: 0min-1.5min, 10% B; 1.5min-2min, 10% -30% B; 2min-3min, 30% -55% B; 3min-6min, 55% -65% B; 6min-7min, 65% -70% B; 7min-8min, 70% B; 8-12min, 70-72% B; 12min-13min, 72% -75% B; 13min-14min, 75% -90% B; 14min-14.1min, 90% -10% B; 14.1-16min, 10% B.
3. The method of claim 1, wherein the method is performed according to the following conditions:
flow rate: 0.2mL/min-0.4 mL/min;
sample introduction amount: 3-7 muL;
column temperature: 28-32 ℃.
4. The method of claim 3, wherein the method is performed according to the following conditions:
flow rate: 0.3 mL/min;
sample introduction amount: 5 muL;
column temperature: at 30 ℃.
5. The method of claim 1, wherein the mass spectrometry is performed according to the following conditions:
an ion source: an electrospray ion source;
scanning mode: a negative ion mode;
detection mode: monitoring multiple reactions;
spraying voltage: 3400V-3600V;
evaporation temperature: 370-390 ℃;
ion transfer tube temperature: 315-335 ℃;
sheath gas: nitrogen, 35Arb-45 Arb;
auxiliary gas: nitrogen, 3Arb-10 Arb;
collision gas: argon, 1mTorr-3 mTorr.
6. The method of claim 5, wherein the method performs mass spectrometry according to the following conditions:
an ion source: an electrospray ion source;
scanning mode: a negative ion mode;
detection mode: monitoring multiple reactions;
spraying voltage: 3500V;
evaporation temperature: 380 ℃;
ion transport tube temperature: 325 ℃;
sheath gas: nitrogen, 40 Arb;
auxiliary gas: nitrogen, 5 Arb;
collision gas: argon, 1.5 mTorr.
7. The method of claim 1, wherein the organic solvent is methanol in the preparation of the standard solution.
8. The method according to claim 1, wherein the concentrations of BPE, BPA, BPB, BPF, TBBPA, BPC, BPG, DMBPA and BPOPPA in the standard solution are all 1.0 μ g/L-200.0 μ g/L, the concentrations of BPAP, BPBP and BPP are all 0.2 μ g/L-40.0 μ g/L, and the concentrations of BPS and BPAF are all 0.05 μ g/L-10.0 μ g/L.
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