CN105203659B - The assay method of the methoxy benzophenone of 2 hydroxyl 4 in a kind of dry food analogies - Google Patents

The assay method of the methoxy benzophenone of 2 hydroxyl 4 in a kind of dry food analogies Download PDF

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CN105203659B
CN105203659B CN201510590565.4A CN201510590565A CN105203659B CN 105203659 B CN105203659 B CN 105203659B CN 201510590565 A CN201510590565 A CN 201510590565A CN 105203659 B CN105203659 B CN 105203659B
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dry food
escalol
ion
food analogies
naphthalene
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CN105203659A (en
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罗世鹏
季玮玉
张敏
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CHANGZHOU TESTING AND TECHNICAL CENTER FOR DANGEROUS GOODS AND PACKAGING
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CHANGZHOU TESTING AND TECHNICAL CENTER FOR DANGEROUS GOODS AND PACKAGING
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Abstract

The present invention relates to a kind of assay method of the methoxy benzophenone of 2 hydroxyl 4 in dry food analogies, the dry food analogies for taking quality to be m are produced containing naphthalene d8Test fluid and produce standard working solution and go forward side by side the triple level Four bar Mass Spectrometer Methods of promoting the circulation of qi phase chromatographic tandem, according to correction factor formula f=(AIS×mi)/(Ai×mI) and formula X=(A × mS×f)/(AS× m) try to achieve the content of the methoxy benzophenone of 2 hydroxyl 4 in dry food analogies, final result can reduce error by parallel test, the present invention establishes the detection method of the methoxy benzophenone migration amount of 2 hydroxyl 4 in dry food analogies first, the measuring method is direct injected after the concentrated filter membrane of sample extracting solution, it is not necessary to carries out the pre-treatment steps such as the derivatization of complexity.

Description

The measure of ESCALOL 567 in a kind of dry food analogies Method
Technical field
The present invention relates to a kind of assay method of ESCALOL 567 in dry food analogies.
Background technology
2009, European Union's food and the quick early warning system of feed class (RASFF) have advertised oatmeal and printed by packaging for foodstuff 4- methyl benzophenones (4-MBP) and the event of benzophenone (BP) pollution in brush ink, this shows that dry food may also meet with Polluted by the contact material such as packing.Accordingly, European Union's food chain and animal health standing committee have formulated a variety of benzophenone The maximum migration limitation of the printing-ink packaging for foodstuff of photoinitiator is, it is specified that 2- hydroxyls in packaging for foodstuff printing-ink material The migration limitation of base -4- methyl benzophenones is 6.0mg/kg, and China GB 9685 is equally provided, in plastic-food contact material The migration limitation of 2- hydroxy-4-methyl benzophenone is 6.0mg/kg.2011, the plastics regulation (EU) that EU Committee puts into effect Then clear stipulaties are used for the dry foods such as starch, cereal, dried noodle, solid-state carbohydrate, nut, milk powder, bread in No.10/2011 Food simulants be that modified poly- (2,6- diphenyl-p-phenylene) is used as dry food analogies.At present both at home and abroad for dryness There is not been reported for the detection of 2- hydroxy-4-methyls benzophenone migration amount in food simulants.Therefore dry food simulation is established The quantitative detecting method of 2- hydroxy-4-methyls benzophenone migration amount in thing, can be effectively to the health of food contact material Performance is tested supervision, so as to protect the health and safety of people.
In analyte detection process, the accuracys of quantitative analysis results and sample pre-treatments step and chromatographic mass spectrometry condition Select closely bound up, not exclusively optimal chromatogram measuring condition is just can determine that by limited experiment, if to analysis inspection The setting of survey condition has deviateed, then very big error may be caused to quantitative testing result, in addition can obtain false positive or The testing result completely contradicted.
The content of the invention
2- hydroxyl -4- first in the dry food analogies that precision is high, error is small is checked it is an object of the invention to provide a kind of The assay method of epoxide benzophenone.
Realize that the technical scheme of the object of the invention is as follows：
The assay method of ESCALOL 567 in a kind of dry food analogies, it is characterised in that：Including Following steps,
Step 1, takes the dry food analogies that quality is m, and addition contains known quality mSNaphthalene-d8Solvent extraction Constant volume is concentrated after filter again and obtains test fluid；
Step 2, to test fluid carry out the triple level Four bar Mass Spectrometer Methods of gas-chromatography-series connection, take gained instrument to naphthalene- d8Response signal is internal standard peak area AS, the instrument for taking gained is test specimens to ESCALOL 567 response signal Product peak area A；
Step 3, standard working solution is produced, prepare one group with containing quality mINaphthalene-d82- hydroxyl -4- the first of internal standard compound Epoxide benzophenone standard working solution, the triple level Four bar mass spectrums of gas-chromatography-series connection are then carried out to standard working solution and are examined Survey, according to the naphthalene-d obtained by detection8It is quantitative from value peak area AISAnd corresponding quality mI, resulting with reference to detection ESCALOL 567 quota ion peak area AiAnd corresponding quality mi, then calculated and corrected according to formula The factor f, f=(AIS×mi)/(Ai×mI)；
Step 4, by step 2 with resulting testing result ASAnd sample quality m in A, and step 1 and added Internal standard quality mS, with reference to correction factor f resulting in step 3 and then according to formula X=(A × mS×f)/(AS× m) calculate Draw the content X of ESCALOL 567 in dry food analogies1, wherein：
X represents the content of ESCALOL 567 in dry food analogies, unit mg/kg.
Step 5, repeat step one to step 4 carry out parallel test, obtain replicate test result X2, to test knot twice The arithmetic mean of instantaneous value of fruit, i.e. X=(X1+X2)/2 are used as test result；
The ion gun used in triple level Four bar Mass Spectrometer Methods of being connected in step 2 and step 3 is electron impact ion source Or chemical ionization source, the ion source temperature are 230-260 DEG C, electron energy 65-75eV；
The carrier gas used in triple level Four bar Mass Spectrometer Methods of being connected in step 2 and step 3 for purity be 99%~ 99.9999% helium, carrier gas control model are constant voltage mode, constant current mode or constant linear velocity pattern, and collision gas is purity 99%~99.999% nitrogen；
Solvent delay 3-6min in triple level Four bar Mass Spectrometer Methods of being connected in step 2 and step 3；
Detection mode is full scan, selection ion scan in triple level Four bar Mass Spectrometer Methods of being connected in step 2 and step 3 Or multiion reaction monitoring, triple level Four bar Mass Spectrometer Method intermediate-resolutions of connecting in step 2 and step 3 use unit, wide Or widest resolution ratio；
In step 2, the detection parameters setting of related gas chromatography tandem mass spectrometry is as follows：
Select 136.1---->108.1*m/z, collision energy are 10~30eV and 136.1---->81.9m/z, impact energy Two pairs of ions for 30~50eV are measured as internal standard compound naphthalene-d8Monitoring ion；Select 226.9---->184*m/z, impact energy Measure as 10~30eV and 226.9---->128m/z, two pairs of ions that collision energy is 30~50eV are as 2- hydroxyl -4- methoxies Base benzophenone monitors ion, and the ion with * is quota ion, and remaining is qualitative daughter ion；
In step 2 and step 3, chromatographic column coating is polyethylene glycol, polystyrene or polymethyl siloxane material, chromatogram Column length is 30-60m, and chromatogram column internal diameter is 0.18mm-0.25mm, and coating thickness is 0.20-0.30 μm, sample size 0.5- 2.0 μ L, 80-110 DEG C of the initial temperature of gas-chromatography, 0-4min is kept, 220-280 is warming up to 15-25 DEG C/min speed DEG C, keep 3-8min, flow rate of carrier gas 0.8-1.2mL/min.
The present invention is under ion gun to internal standard compound naphthalene-d8And ESCALOL 567 is cracked, obtain Both one-level cracking peaks, then carry out two level cracking to one-level fragment, and second order mses fragment is analyzed, and the present invention is first The secondary detection method for establishing ESCALOL 567 migration amount in dry food analogies, the measuring method For direct injected after the concentrated filter membrane of sample extracting solution, it is not necessary to carry out the pre-treatment steps such as the derivatization of complexity.
Preferably, it is convenient to extract 2- hydroxyls -4- methoxyl group hexichol therein in order that dry food analogies are uniformly dissolved Ketone, in step 1 during solution dry food analogies, using containing naphthalene-d8Methanol solution dissolved, in course of dissolution Ultrasonic instrument 5-60min is opened, temperature control carries out one again to filter residue after 0-100 DEG C, preliminarily solubilised filtering with methanol solution Secondary dissolution filter operation, the solution being filtrated to get twice concentrates constant volume 1-10mL, and excessively organic filter membrane again after merging, described organic Filter sizes are 0.1 μm -0.45 μm.
Preferably, in order to reduce the error of testing result, the allowable error of parallel test is 20% in step 5.
Preferably, in order to ensure the accuracy of standard working solution, the standard working solution in step 3 is more than by content 99.0% ESCALOL 567 standard items and content are more than 99.0% naphthalene-d8Standard items and chromatographically pure first Alcohol dissolving constant volume is made.
According to the solution treatment conditions after optimizing in the present invention and the setting of optimal chromatogram mass spectrometry parameters, can accurately survey Measure ESCALOL 567 migration amount in dry food analogies, strong interference immunity, the quantitative result degree of accuracy Height, reappearance is good, and test limit disclosure satisfy that the limitation of 5.0mg/kg in European Union and Chinese GB 9685 up to 0.05mg/kg It is required that.
Embodiment
The assay method of ESCALOL 567, comprises the following steps in a kind of dry food analogies,
Step 1,1g dry food analogies are taken in conical flask, add 50mL and contain 0.5 μ g naphthalenes-d8Methanol solution, Ultrasonic dissolution 30min, solution are filtered after fully quickly dissolving at 50 DEG C in course of dissolution, and filter residue is washed with methanol solution, are closed And filtrate, and concentrate and be settled to 5.0mL, cross the organic filter membranes of 0.2um and obtain test fluid；
Step 2, to test fluid carry out the triple level Four bar Mass Spectrometer Methods of gas-chromatography-series connection, take gained instrument to naphthalene- d8Response signal is internal standard peak area AS, the instrument for taking gained is test specimens to ESCALOL 567 response signal Product peak area A；
Step 3, standard working solution is produced, prepare one group and the naphthalene-d containing 0.5 μ g8Internal standard compound and 0.5 μ g 2- hydroxyls Base -4- methoxy benzophenone standard working solutions, the triple level Four bars of gas-chromatography-series connection then are carried out to standard working solution Mass Spectrometer Method, according to the naphthalene-d obtained by detection8It is quantitative from value peak area AISAnd corresponding quality mI0.5 μ g, with reference to ESCALOL 567 quota ion peak area A obtained by detectioniAnd corresponding quality mi0.5 μ g, so Correction factor f is calculated according to formula afterwards；F=(AIS×0.5)/(Ai×0.5)
Wherein, in gas chromatographic detection, chromatographic column coating is polyethylene glycol, polystyrene or polymethyl siloxane material, Chromatogram column length is 30-60m, and chromatogram column internal diameter is 0.18mm-0.25mm, and coating thickness is 0.20-0.30 μm, and sample size is 0.5-2.0 μ L, 80-110 DEG C of the initial temperature of gas-chromatography, 0-4min is kept, 220- is warming up to 15-25 DEG C/min speed 280 DEG C, keep 3-8min, flow rate of carrier gas 0.8-1.2mL/min；
The ion gun used in triple level Four bar Mass Spectrometer Methods of connecting is described for electron impact ion source or chemical ionization source Ion source temperature is 230-260 DEG C, electron energy 65-75eV, and carrier gas is the helium that purity is 99%~99.9999%, is carried Gas control model is constant voltage mode, constant current mode or constant linear velocity pattern, and collision gas is the nitrogen of purity 99%~99.999%, Detection mode is full scan, selection ion scan or multiion reaction monitoring, solvent delay 3-6min, resolution ratio using unit, Wide or widest resolution ratio；
Select 226.9---->184 and 226.9---->128 two pairs of ions are as internal standard compound naphthalene-d8Monitoring ion；Choosing Select 226.9---->184 and 226.9---->Monitoring ion of 128 two pairs of ions as ESCALOL 567；
Step 4, by testing result A resulting in step 2SWith the sample quality m in A and step 1 and added interior Mark amount of substance mS0.5 μ g, with reference to correction factor f resulting in step 3 and then according to formula X=(A × mS×f)/(AS×m) The content X of ESCALOL 567 in dry food analogies is calculated1, wherein：
mSFor naphthalene-d in test fluid8Quality, 0.5 μ g,
M be dry food analogies quality, 1g,
X represents the content of ESCALOL 567 in dry food analogies, unit mg/kg.
Step 5, repeat step one to step 4 carry out parallel test, obtain replicate test result X2, to test knot twice The arithmetic mean of instantaneous value of fruit, i.e. X=(X1+X2)/2 are used as test result.
In implementation process of the present invention, collision energy is shown in such as table 1 below：
Naphthalene-the d of table 18With the collision energy of ESCALOL 567
The present invention establishes the detection side of ESCALOL 567 migration amount in dry food analogies first Method, the measuring method are direct injected after the concentrated filter membrane of sample extracting solution, it is not necessary to before carrying out derivatization of complexity etc. Processing step, ESCALOL 567 migration amount, anti-interference in dry food analogies can be accurately measured By force, the quantitative result degree of accuracy is high, and reappearance is good.
It is below the preferred parameter in the specific embodiment of the present invention：
GC conditions：
1) chromatographic column：Coating is polymethyl siloxane material, chromatogram column length 30m；Chromatogram column internal diameter is 0.25mm；Apply Film thickness is：0.25μm；
2) sample size：1.0μL；
3) temperature programming condition：100 DEG C of initial temperature, 3min is kept, be warming up to 280 DEG C with 15 DEG C/min speed, protect Hold 5min；
4) flow rate of carrier gas：1.0mL/min.
Series connection triple quadrupole bar Mass Spectrometry Conditions：
1) ion gun:Electron bombardment (EI)；
2) ion source temperature：250℃；
3) electron energy：70eV；
4) carrier gas control model：Constant current mode；
5) detection mode：Full scan (SCAN), selection ion scan (SIM) or multiion reaction monitoring (MRM)；
6) solvent delay：4min；
7) carrier gas：Purity is 99.9992% helium；
8) heating-up temperature is aided in：300℃；
9) collision gas：The nitrogen of purity 99.999%；
10) resolution ratio：Unit resolution ratio；
11) collision energy is shown in such as table 2 below：
Naphthalene-the d of table 28With the collision energy of ESCALOL 567
The precision of this method and the rate of recovery are detected using additive process：
Add 2- hydroxyl -4- methoxies respectively in the dry food analogies without ESCALOL 567 Base benzophenone be tri- levels of 0.05mg/kg, 0.50mg/kg, 5.00mg/kg after by the present invention step carry out sample before locate Manage and determine, each horizontal repetition is added and determined 6 times, and carries out the rate of recovery and precision calculating, the rate of recovery and precision Result of the test refers to table 3.
The ESCALOL 567 of table 3 TIANZHU XINGNAO Capsul and precision in dry food analogies
As can be seen from Table 3, the rate of recovery of this method and precision are good.The rate of recovery that method determines to all kinds of analogies Up to 89%~98%；Precision is less than 8%, and accurately and reliably, precision is high for quantitative result.
The present invention, which is can be seen that, from above-described embodiment and accuracy test establishes 2- hydroxyls in dry food analogies first The detection method of base -4- methoxy benzophenone migration amounts, the measuring method are straight after the concentrated filter membrane of sample extracting solution Tap into sample, it is not necessary to carry out the pre-treatment steps such as the derivatization of complexity.In addition, according in the present invention optimize after Pretreatment, And the setting of optimal chromatogram mass spectrometry parameters, 2- hydroxyls -4- methoxyl group hexichol in dry food analogies can be accurately measured Ketone migration amount, strong interference immunity, the quantitative result degree of accuracy is high, and reappearance is good, and test limit is up to 0.05mg/kg, Neng Gouman 5.0mg/kg limitation requirement in sufficient European Union and Chinese GB 9685.
The preferred embodiment of invention is the foregoing is only, is not intended to limit the scope of the invention, it is every to utilize this The equivalent structure or equivalent flow conversion that description of the invention and accompanying drawing content are made, or directly or indirectly it is used in other correlations Technical field, it is included within the scope of the present invention.

Claims (4)

  1. A kind of 1. assay method of ESCALOL 567 in dry food analogies, it is characterised in that：Including with Lower step,
    Step 1, takes the dry food analogies that quality is m, and addition contains known quality mSNaphthalene-d8Solvent extraction filtering after Constant volume is concentrated again obtains test fluid；
    Step 2, the triple level Four bar Mass Spectrometer Methods of gas-chromatography-series connection are carried out to test fluid, take the instrument of gained to naphthalene-d8Response Signal is internal standard peak area AS, the instrument for taking gained is test sample peak to ESCALOL 567 response signal Area A；
    Step 3, standard working solution is produced, prepare one group with containing quality mINaphthalene-d82- hydroxyl -4- the methoxyl groups of internal standard compound Benzophenone standard working solution, the triple level Four bar Mass Spectrometer Methods of gas-chromatography-series connection, root then are carried out to standard working solution According to the naphthalene-d obtained by detection8It is quantitative from value peak area AISAnd corresponding quality mI, with reference to the 2- hydroxyls obtained by detection Base -4- methoxy benzophenone quota ion peak areas AiAnd corresponding quality mi, correction factor is then calculated according to formula F, f=(AIS×mi)/(Ai×mI)；
    Step 4, by step 2 with resulting testing result ASAnd the sample quality m in A, and step 1 and added internal standard matter Measure mS, with reference to correction factor f resulting in step 3 and then according to formula X=(A × mS×f)/(AS× m) be calculated it is dry The content X of ESCALOL 567 in property food simulants1, wherein：
    X represents the content of ESCALOL 567 in dry food analogies, unit mg/kg；
    Step 5, repeat step one to step 4 carry out parallel test, obtain replicate test result X2, with test result twice Arithmetic mean of instantaneous value, i.e. X=(X1+X2)/2 are used as test result；
    The ion gun used in triple level Four bar Mass Spectrometer Methods of being connected in step 2 and step 3 is electron impact ion source or change Ionization source is learned, the ion source temperature is 230-260 DEG C, electron energy 65-75eV；
    The carrier gas used in triple level Four bar Mass Spectrometer Methods of being connected in step 2 and step 3 is 99%~99.9999% for purity Helium, carrier gas control model is constant voltage mode, constant current mode or constant linear velocity pattern, collision gas be purity 99%~ 99.999% nitrogen；
    Solvent delay 3-6min in triple level Four bar Mass Spectrometer Methods of being connected in step 2 and step 3；
    Detection mode is full scan, selection ion scan or more in triple level Four bar Mass Spectrometer Methods of being connected in step 2 and step 3 Ionic reaction detects, triple level Four bar Mass Spectrometer Method intermediate-resolutions of connecting in step 2 and step 3 using unit, wide or Widest resolution ratio；
    In step 2, the detection parameters setting of related gas chromatography tandem mass spectrometry is as follows：
    Select 136.1---->108.1*m/z, collision energy are 10~30eV and 136.1---->81.9m/z, collision energy are 30~50eV two pairs of ions are as internal standard compound naphthalene-d8Monitoring ion；Select 226.9---->184*m/z, collision energy are 10~30eV and 226.9---->128m/z, two pairs of ions that collision energy is 30~50eV are as 2- hydroxyl -4- methoxyl groups two Benzophenone monitors ion, and the ion with * is quota ion, and remaining is qualitative daughter ion；
    In step 2 and step 3, chromatographic column coating is polyethylene glycol, polystyrene or polymethyl siloxane material, column length It is 0.18mm-0.25mm to spend for 30-60m, chromatogram column internal diameter, and coating thickness is 0.20-0.30 μm, and sample size is 0.5-2.0 μ L, 80-110 DEG C of the initial temperature of gas-chromatography, 0-4min is kept, be warming up to 220-280 DEG C with 15-25 DEG C/min speed, keep 3-8min, flow rate of carrier gas 0.8-1.2mL/min.
  2. 2. the measure side of ESCALOL 567 in a kind of dry food analogies according to claim 1 Method, it is characterised in that：In step 1 during solution dry food analogies, using containing naphthalene-d8Methanol solution dissolved, it is molten Ultrasonic instrument 5-60min is opened in solution preocess, temperature control is carried out once again after 0-100 DEG C, preliminarily solubilised filtering to filter residue Dissolution filter operates, and the solution being filtrated to get twice concentrates constant volume 1-10mL, and excessively organic filter membrane again after merging, described to have machine filter Membrane aperture is 0.1 μm -0.45 μm.
  3. 3. the measure side of ESCALOL 567 in a kind of dry food analogies according to claim 1 Method, it is characterised in that：The allowable error of parallel test is 20% in step 5.
  4. 4. the measure side of ESCALOL 567 in a kind of dry food analogies according to claim 1 Method, it is characterised in that：Standard working solution in step 3 is more than 99.0% ESCALOL 567 by content Standard items and content are more than 99.0% naphthalene-d8Standard items and Chromatographic Pure Methanol dissolving constant volume are made.
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CN106226413A (en) * 2016-07-06 2016-12-14 常州工学院 The assay method of the tert-butyl group 4 hydroxyanisol in a kind of dry food analogies
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