CN107247097A - Bisphenol-A, Bisphenol F, the method for bisphenol S content can be detected simultaneously - Google Patents

Bisphenol-A, Bisphenol F, the method for bisphenol S content can be detected simultaneously Download PDF

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Publication number
CN107247097A
CN107247097A CN201710408509.3A CN201710408509A CN107247097A CN 107247097 A CN107247097 A CN 107247097A CN 201710408509 A CN201710408509 A CN 201710408509A CN 107247097 A CN107247097 A CN 107247097A
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Prior art keywords
bisphenol
sample
ion
detect
content simultaneously
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Inventor
张利娟
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Shenzhen Intertek Quality Technology Service Co Ltd
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Shenzhen Intertek Quality Technology Service Co Ltd
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Priority to CN201710408509.3A priority Critical patent/CN107247097A/en
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    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02Column chromatography

Abstract

Proposed by the present invention to detect bisphenol-A, Bisphenol F, the method for bisphenol S content simultaneously, method includes being pre-processed in sample, obtains sample to be checked;The sample to be checked is detected using LC MS/MS, the one or more in bisphenol-A, Bisphenol F, bisphenol S content are obtained.Energy of the invention is quick, accurate, Simultaneous Determination bisphenol-A, Bisphenol F, three kinds of materials of bisphenol S, and minimum detection limit detects time saving, reduce the workload of testing staff up to 0.01mg/kg, it is easy to accomplish mass processing, so as to greatly improve detection efficiency;Consumptive material toxicity used is low, and extraction agent usage amount is few, reduces the exposure risk of tester, while greatly reducing the cost of consumptive material consumption and liquid waste processing.

Description

Bisphenol-A, Bisphenol F, the method for bisphenol S content can be detected simultaneously
Technical field
The present invention relates to Instrumental Analysis field, especially relating to one kind can be while detects bisphenol-A, Bisphenol F, bisphenol S The method of content.
Background technology
In food contact material field, bisphenol S is as the substitute of bisphenol-A, and its security also enjoys people's always Concern.
Research shows that the female hormone influence that bisphenol S is produced on organism is similar with bisphenol-A, is also that a kind of endocrine is done Plain (Environmental Hormone) is disturbed, with the harm for upsetting reproductive system.The measure of bisphenol S (BPS) migration amount is to evaluate food contact The Scientific Approaches of material safety.China GB 9685-2016《National food safety standard food contact material and product are with adding Plus agent uses standard》The migration limitation for providing bisphenol S in food simulants is 0.05mg/kg.
Bisphenol F, also known as 4,4 dihydroxydiphenyl methane are a kind of synthetic material monomers.Available for synthesizing epoxy tree Fat, polycarbonate resin, polyester resin He Fen Chuo resins, fire retardant, antioxidant and surfactant etc..
CN201310105282 discloses the purifying of a kind of packaging material for food and container migration stain thing bisphenol Preprocess method is enriched with, this method comprises the following steps:C18 reverse phase solid phase extractions pillar through methanol and ultra-pure water activation after on Sample, is first eluted with 20% methanol aqueous solution, and again with methanol elution, eluent is dried up through nitrogen, and residue, filtering are redissolved with acetonitrile Liquid chromatogram-fluorescence detector detection is carried out afterwards.Using the preconditioning technique, 6 kinds of bisphenols (bisphenol-A (BPA), bisphenol bs (BPB), bis-phenol E (BPE), Bisphenol F (BPF), bisphenol A diglycidyl ether (BADGE) and Bisphenol F diglycidyl ether (BFDGE) rate of recovery) is between 75.92%~102.10%, and relative deviation is below 5%, and the degree of accuracy and precision are good.
CN201410247394 discloses a kind of assay method of bisphenol S migration amount in plastic food packaging materials, including [step 1] prepares standard working solution, food simulants test solution and blank test solution;[step 2] uses high performance liquid chromatography-series connection Triple quadrupole bar GC-MS carries out the triple level Four bar mass spectrums of liquid chromatogram-series connection to three kinds of solution of step one and surveyed respectively It is fixed;The concentration x of bisphenol S using in standard working solution is abscissa, using the corresponding quota ion peak area y measured as vertical seat Mark, draws standard working solution regression curve, and the linear equation y=ax+b obtained according to curve calculates the oblique of regression curve Rate a and intercept b;[step 3] calculates bisphenol S concentration in food simulants test solution according to formula c=[(y moulds-y is empty)-b]/a.Should Method can accurately measure the migration amount of bisphenol S in plastic food packaging materials, quantify accurately and reliably, and reappearance is good.
However, CN201310105282 belongs to the improvement to sample pretreatment process, and it is cumbersome, take long; CN201410247394 can only analyze bisphenol S, though analysis time has shortened, and it is still not ideal enough.
The content of the invention
The main object of the present invention can detect bisphenol-A, Bisphenol F, the method for bisphenol S content simultaneously to provide, can be significantly Ground reduces detection time, improves detection efficiency.
Present invention proposition is a kind of can to detect bisphenol-A, Bisphenol F, the method for bisphenol S content simultaneously, comprise the following steps:
Sample is pre-processed, sample to be checked is obtained;
The sample to be checked is detected using LC-MS/MS, one kind in bisphenol-A, Bisphenol F, bisphenol S content is obtained Or it is a variety of;
Wherein, LC-MS/MS liquid-phase condition is:
Liquid-phase chromatographic column:ACQUITYUPLC HSS or suitable chromatographic columns, a diameter of 1.8 μm of filler;Chromatogram column length is 100mm;Chromatogram column internal diameter is 2.1mm;
Flow phase composition and elution requirement:The acetonitrile and one-level water of chromatographically pure rank, condition of gradient elution is:
0min, 40% water, 60% acetonitrile;
3min, 40% water, 60% acetonitrile;
Sample size:1μL;
Column temperature:40℃;
Flow velocity:0.35mL/min;
Mass Spectrometry Conditions are:
Ion gun:ESI, Ionization mode ES (-);
Capillary voltage:3.4kV;
Taper hole voltage:35.0V;
Collide cell voltage:3.55V;
Analyzer voltage:2.35V;
Ion source temperature:150℃
Desolvation temperature:500℃;
Scan pattern:Multiple-reaction monitoring (MRM);
Collision energy is:
Bisphenol-A:Quota ion includes the daughter ion that m/z is 212, and collision energy is 27eV, and qualitative ion is including m/z 133 daughter ion, collision energy is 13eV;
Bisphenol F:Quota ion includes the daughter ion that m/z is 105, and collision energy is 22eV, and it is 93 that qualitative ion, which includes m/z, Daughter ion, collision energy is 30eV;
Bisphenol S:Quota ion includes the daughter ion that m/z is 108, and collision energy is 26eV, and it is 92 that qualitative ion, which includes m/z, Daughter ion, collision energy is 34eV.
Preferably, the sample is food contact material.
Preferably, the sample is food contact plastic products.
Preferably, it is described to be pre-processed sample, before acquisition sample to be checked, in addition to:
Set up the hybrid standard concentration curve of bisphenol-A, Bisphenol F, bisphenol S.
Preferably, it is described to set up bisphenol-A, Bisphenol F, bisphenol S hybrid standard concentration curve, including:
With 50%V/V ethanol prepare ultimate density be 0.01mg/kg, 0.02mg/kg, 0.05mg/kg, 0.10mg/kg, 0.20mg/kg bisphenol-A, Bisphenol F, bisphenol S hybrid standard working solution, then it is separately added into internal standard substance bisphenol-A-D16, bis-phenol A-D16 concentration is 0.02mg/kg, is quantified by internal standard method, sets up the hybrid standard concentration of bisphenol-A, Bisphenol F, bisphenol S Curve.
Preferably, the bisphenol-A, Bisphenol F, the linearly dependent coefficient of bisphenol S hybrid standard concentration curve are all higher than 0.998。
Preferably, in addition to:
Bisphenol-A, Bisphenol F, bisphenol S mixture that concentration is 0.01mg/kg are added in blank sample matrix, is then determined Bisphenol-A, Bisphenol F, the content of bisphenol S, calculate the rate of recovery, bisphenol-A, Bisphenol F, the rate of recovery of bisphenol S 90% to 110% it Between.
Preferably, it is described to be pre-processed sample, sample to be checked is obtained, including:
Take 1dm2Sample is in beaker, and addition is pre-heated to 70 DEG C of 50%V/V ethanol simulated solution 167mL, uses glass dish Beaker is covered, and is transferred to and is pre-heated in 70 DEG C of baking oven, 2h is placed, then beaker is taken out, sample is removed immediately, then take Appropriate simulated solution, is filtered, the liquid being transferred in sample bottle, sample bottle is sample to be checked through 0.22 μm of nylon leaching film.
Preferably, the lowest detection of methods described is limited to 0.01mg/kg.
Preferably, the detection time of methods described is 3min.
It is proposed by the present invention to detect bisphenol-A, Bisphenol F, the method for bisphenol S content simultaneously, can be quick, accurate, simultaneously fixed Bisphenol-A, Bisphenol F, three kinds of materials of bisphenol S are determined in measurement, and minimum detection limit detects time saving, reduce detection people up to 0.01mg/kg The workload of member, it is easy to accomplish mass processing, so as to greatly improve detection efficiency;Consumptive material toxicity used is low, extraction agent Usage amount is few, reduces the exposure risk of tester, while greatly reducing the cost of consumptive material consumption and liquid waste processing.
Brief description of the drawings
Fig. 1 can detect bisphenol-A, Bisphenol F, the schematic flow sheet of the embodiment of method one of bisphenol S content simultaneously for the present invention;
Fig. 2 is the standard concentration curve of bisphenol-A;
Fig. 3 is the standard concentration curve of Bisphenol F;
Fig. 4 is the standard concentration curve of bisphenol S;
Fig. 5 is the chromatogram of bisphenol-A;
Fig. 6 is the chromatogram of Bisphenol F;
Fig. 7 is the chromatogram of bisphenol S.
The realization, functional characteristics and advantage of the object of the invention will be described further referring to the drawings in conjunction with the embodiments.
Embodiment
It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, it is not intended to limit the present invention.
Reference picture 1, present invention proposition is a kind of can to detect bisphenol-A, Bisphenol F, the method for bisphenol S content simultaneously, including following Step:
S10, sample pre-processed, obtain sample to be checked;
S20, using LC-MS/MS the sample to be checked is detected, obtained in bisphenol-A, Bisphenol F, bisphenol S content It is one or more.
In step S10, preprocess method can refer to GB 5009.156-2016《National food safety standard food contacts material Material and product migration test preprocess method general rule》And GB31604.1-2015《National food safety standard food contact material And product migration test general rule》, suitable food simulated solution, test temperature, testing time and test specimens liquor ratio are selected, is carried out Migration test.
In step S20, LC-MS/MS liquid-phase condition is:
1) liquid-phase chromatographic column:ACQUITYUPLC HSS or suitable chromatographic columns, a diameter of 1.8 μm of filler;Chromatogram column length is 100mm;Chromatogram column internal diameter is 2.1mm;
2) flowing phase composition and elution requirement:The acetonitrile and one-level water of chromatographically pure rank, the condition of gradient elution such as institute of table 1 Show;
3) sample size:1μL;
4) column temperature:40℃;
5) flow velocity:0.35mL/min.
The liquid chromatogram elution requirement of table 1
Mass Spectrometry Conditions are:
1) ion gun:ESI, Ionization mode ES (-);
2) capillary voltage:3.4kV;
3) taper hole voltage:35.0V;
4) cell voltage is collided:3.55V;
5) analyzer voltage:2.35V;
6) ion source temperature:150℃
7) desolvation temperature:500℃;
8) scan pattern:Multiple-reaction monitoring (MRM);
9) collision energy is shown in Table 2-4;
The collision energy of the bisphenol-A of table 2
The collision energy of the Bisphenol F of table 3
The collision energy of the bisphenol S of table 4
Following examples are specific continuous mode:
First, the hybrid standard concentration curve of bisphenol-A, Bisphenol F, bisphenol S is set up.
With 50%V/V ethanol prepare ultimate density be 0.01mg/kg, 0.02mg/kg, 0.05mg/kg, 0.10mg/kg, 0.20mg/kg bisphenol-A (is represented, CAS with BPA:80-05-7), Bisphenol F (is represented, CAS with BPF:620-92-8), bisphenol S (represented with BPS, CAS:80-09-1) hybrid standard working solution, then internal standard substance bisphenol-A-D16 is separately added into (with BPA-D16 Represent, CAS:96210-87-6), bisphenol-A-D16 concentration is 0.02mg/kg, is quantified by internal standard method.
Bisphenol-A, Bisphenol F, the hybrid standard concentration curve difference of bisphenol S are as shown in figs. 2 to 4.By Fig. 2~4 it can easily be seen that Bisphenol-A, Bisphenol F, the linearly dependent coefficient of bisphenol S hybrid standard concentration curve are all higher than 0.998, meet quantitative requirement.
Followed by sample measuring liquid is treated in preparation, process is as follows:
Take 1dm2Sample is in beaker, and addition is pre-heated to 70 DEG C of 50%V/V ethanol simulated solution 167mL, uses glass dish Beaker is covered, and is transferred to and is pre-heated in 70 DEG C of baking oven, 2h is placed.The sample that the present embodiment is used is moulded for food contact Material products.Then beaker is taken out, sample is removed immediately, then take appropriate simulated solution, filtered, be transferred to through 0.22 μm of nylon leaching film Sample measuring liquid is treated in sample bottle, acquisition.
Followed by sample measuring liquid examination with computer is treated, specific condition of work uses liquid-phase condition and matter in above-mentioned steps S20 Spectral condition.
Bisphenol-A, Bisphenol F, the chromatogram of bisphenol S are obtained as stated above, respectively as shown in Fig. 5~7.Can be with by Fig. 5~7 Find out, bisphenol-A, Bisphenol F, bisphenol S appearance time interval it is larger, do not overlap, thus can measure simultaneously.
The compound target thing that concentration is 0.01mg/kg is added in blank sample matrix, the method that the present invention is provided is entered Row verification.As a result show, bisphenol-A, Bisphenol F, the rate of recovery of bisphenol S are as follows, between 90% to 110%, it is fixed to fully meet Measure the requirement of examination.
Empirical tests, method provided in an embodiment of the present invention, lowest detection is limited to 0.01mg/kg, and detection time is 3min.
It is proposed by the present invention to detect bisphenol-A, Bisphenol F, the method for bisphenol S content simultaneously, can be quick, accurate, simultaneously fixed Bisphenol-A, Bisphenol F, three kinds of materials of bisphenol S are determined in measurement, and minimum detection limit detects time saving, reduce detection people up to 0.01mg/kg The workload of member, it is easy to accomplish mass processing, so as to greatly improve detection efficiency;Consumptive material toxicity used is low, extraction agent Usage amount is few, reduces the exposure risk of tester, while greatly reducing the cost of consumptive material consumption and liquid waste processing.
The preferred embodiments of the present invention are the foregoing is only, are not intended to limit the scope of the invention, it is every to utilize Equivalent structure or equivalent flow conversion that description of the invention is made, or directly or indirectly it is used in other related technology necks Domain, is included within the scope of the present invention.

Claims (10)

1. a kind of can detect bisphenol-A, Bisphenol F, the method for bisphenol S content simultaneously, it is characterised in that comprise the following steps:
Sample is pre-processed, sample to be checked is obtained;
The sample to be checked is detected using LC-MS/MS, bisphenol-A, Bisphenol F, one kind in bisphenol S content or many is obtained Kind;
Wherein, LC-MS/MS liquid-phase condition is:
Liquid-phase chromatographic column:ACQUITYUPLC HSS or suitable chromatographic columns, a diameter of 1.8 μm of filler;Chromatogram column length is 100mm; Chromatogram column internal diameter is 2.1mm;
Flow phase composition and elution requirement:The acetonitrile and one-level water of chromatographically pure rank, condition of gradient elution is:
0min, 40% water, 60% acetonitrile;
3min, 40% water, 60% acetonitrile;
Sample size:1μL;
Column temperature:40℃;
Flow velocity:0.35mL/min;
Mass Spectrometry Conditions are:
Ion gun:ESI, Ionization mode ES (-);
Capillary voltage:3.4kV;
Taper hole voltage:35.0V;
Collide cell voltage:3.55V;
Analyzer voltage:2.35V;
Ion source temperature:150℃
Desolvation temperature:500℃;
Scan pattern:Multiple-reaction monitoring (MRM);
Collision energy is:
Bisphenol-A:Quota ion includes the daughter ion that m/z is 212, and collision energy is 27eV, and it is 133 that qualitative ion, which includes m/z, Daughter ion, collision energy is 13eV;
Bisphenol F:Quota ion includes the daughter ion that m/z is 105, and collision energy is 22eV, and qualitative ion includes the son that m/z is 93 Ion, collision energy is 30eV;
Bisphenol S:Quota ion includes the daughter ion that m/z is 108, and collision energy is 26eV, and qualitative ion includes the son that m/z is 92 Ion, collision energy is 34eV.
2. according to claim 1 can detect bisphenol-A, Bisphenol F, the method for bisphenol S content simultaneously, it is characterised in that institute Sample is stated for food contact material.
3. according to claim 1 can detect bisphenol-A, Bisphenol F, the method for bisphenol S content simultaneously, it is characterised in that institute Sample is stated for food contact plastic products.
4. according to claim 1 can detect bisphenol-A, Bisphenol F, the method for bisphenol S content simultaneously, it is characterised in that institute State and pre-processed sample, before acquisition sample to be checked, in addition to:
Set up the hybrid standard concentration curve of bisphenol-A, Bisphenol F, bisphenol S.
5. according to claim 4 can detect bisphenol-A, Bisphenol F, the method for bisphenol S content simultaneously, it is characterised in that institute State and set up bisphenol-A, Bisphenol F, bisphenol S hybrid standard concentration curve, including:
With 50%V/V ethanol prepare ultimate density be 0.01mg/kg, 0.02mg/kg, 0.05mg/kg, 0.10mg/kg, 0.20mg/kg bisphenol-A, Bisphenol F, bisphenol S hybrid standard working solution, then it is separately added into internal standard substance bisphenol-A-D16, bis-phenol A-D16 concentration is 0.02mg/kg, is quantified by internal standard method, sets up the hybrid standard concentration of bisphenol-A, Bisphenol F, bisphenol S Curve.
6. according to claim 4 can detect bisphenol-A, Bisphenol F, the method for bisphenol S content simultaneously, it is characterised in that institute State bisphenol-A, Bisphenol F, the linearly dependent coefficient of bisphenol S hybrid standard concentration curve and be all higher than 0.998.
7. according to claim 1 can detect bisphenol-A, Bisphenol F, the method for bisphenol S content simultaneously, it is characterised in that also Including:
Bisphenol-A, Bisphenol F, bisphenol S mixture that concentration is 0.01mg/kg are added in blank sample matrix, bis-phenol is then determined A, Bisphenol F, the content of bisphenol S, calculate the rate of recovery, bisphenol-A, Bisphenol F, the rate of recovery of bisphenol S are between 90% to 110%.
8. according to claim 1 can detect bisphenol-A, Bisphenol F, the method for bisphenol S content simultaneously, it is characterised in that institute State and pre-processed sample, obtain sample to be checked, including:
Take 1dm2Sample is in beaker, and addition is pre-heated to 70 DEG C of 50%V/V ethanol simulated solution 167mL, and burning is covered with glass dish Cup, and be transferred to and be pre-heated in 70 DEG C of baking oven, 2h is placed, then beaker is taken out, sample is removed immediately, then take appropriate mould Intend liquid, filtered through 0.22 μm of nylon leaching film, the liquid being transferred in sample bottle, sample bottle is sample to be checked.
9. according to claim 1 can detect bisphenol-A, Bisphenol F, the method for bisphenol S content simultaneously, it is characterised in that institute The lowest detection for stating method is limited to 0.01mg/kg.
10. according to claim 1 can detect bisphenol-A, Bisphenol F, the method for bisphenol S content simultaneously, it is characterised in that institute The detection time for stating method is 3min.
CN201710408509.3A 2017-06-02 2017-06-02 Bisphenol-A, Bisphenol F, the method for bisphenol S content can be detected simultaneously Pending CN107247097A (en)

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CN111198242A (en) * 2018-11-19 2020-05-26 广州质量监督检测研究院 Method for determining bisphenol compounds in food simulants
CN111707737A (en) * 2020-05-06 2020-09-25 深圳市农产品质量安全检验检测中心(深圳市动物疫病预防控制中心) Method for improving detection precision of bisphenol A content in animal derived food and application thereof

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CN111198242A (en) * 2018-11-19 2020-05-26 广州质量监督检测研究院 Method for determining bisphenol compounds in food simulants
CN110095422A (en) * 2019-05-24 2019-08-06 山东师范大学 For quickly detecting aptamers, aptamer nanogold material, kit and its application of bisphenol-A
CN111707737A (en) * 2020-05-06 2020-09-25 深圳市农产品质量安全检验检测中心(深圳市动物疫病预防控制中心) Method for improving detection precision of bisphenol A content in animal derived food and application thereof
CN111707737B (en) * 2020-05-06 2022-12-20 深圳市质量安全检验检测研究院(深圳市动物疫病预防控制中心) Method for improving detection precision of bisphenol A content in animal derived food and application thereof

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RJ01 Rejection of invention patent application after publication

Application publication date: 20171013

RJ01 Rejection of invention patent application after publication