CN110133121A - Method that is a kind of while measuring ethylenediamine, propane diamine and hexamethylene diamine the amount of migration in food contact material and product - Google Patents
Method that is a kind of while measuring ethylenediamine, propane diamine and hexamethylene diamine the amount of migration in food contact material and product Download PDFInfo
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- CN110133121A CN110133121A CN201910317506.8A CN201910317506A CN110133121A CN 110133121 A CN110133121 A CN 110133121A CN 201910317506 A CN201910317506 A CN 201910317506A CN 110133121 A CN110133121 A CN 110133121A
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- food
- ethylenediamine
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- migration
- diamine
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- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 title claims abstract description 107
- 235000013305 food Nutrition 0.000 title claims abstract description 93
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 238000013508 migration Methods 0.000 title claims abstract description 52
- 230000005012 migration Effects 0.000 title claims abstract description 52
- 238000000034 method Methods 0.000 title claims abstract description 41
- 239000000463 material Substances 0.000 title claims abstract description 37
- GGHDAUPFEBTORZ-UHFFFAOYSA-N propane-1,1-diamine Chemical compound CCC(N)N GGHDAUPFEBTORZ-UHFFFAOYSA-N 0.000 title claims abstract description 13
- 239000000243 solution Substances 0.000 claims abstract description 44
- 239000012085 test solution Substances 0.000 claims abstract description 30
- 238000001514 detection method Methods 0.000 claims abstract description 17
- 239000007788 liquid Substances 0.000 claims abstract description 16
- PVDVPOZEJCXUAM-UHFFFAOYSA-N acetonitrile;n,n-diethylethanamine Chemical compound CC#N.CCN(CC)CC PVDVPOZEJCXUAM-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000004033 plastic Substances 0.000 claims abstract description 8
- 229920003023 plastic Polymers 0.000 claims abstract description 8
- 238000004364 calculation method Methods 0.000 claims abstract description 4
- 238000002474 experimental method Methods 0.000 claims abstract description 4
- 239000012488 sample solution Substances 0.000 claims abstract description 4
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 claims description 48
- 239000000523 sample Substances 0.000 claims description 31
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 28
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical group CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 27
- 238000012360 testing method Methods 0.000 claims description 23
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 18
- 150000002500 ions Chemical class 0.000 claims description 16
- 239000012086 standard solution Substances 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- VIEUIBSXXCVYNO-UHFFFAOYSA-N acetonitrile isothiocyanatobenzene Chemical compound C(C)#N.C1(=CC=CC=C1)N=C=S VIEUIBSXXCVYNO-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 229960000583 acetic acid Drugs 0.000 claims description 7
- 239000012528 membrane Substances 0.000 claims description 7
- 238000004949 mass spectrometry Methods 0.000 claims description 6
- ALSPKRWQCLSJLV-UHFFFAOYSA-N azanium;acetic acid;acetate Chemical group [NH4+].CC(O)=O.CC([O-])=O ALSPKRWQCLSJLV-UHFFFAOYSA-N 0.000 claims description 5
- 238000005119 centrifugation Methods 0.000 claims description 5
- 150000004985 diamines Chemical class 0.000 claims description 5
- 238000002552 multiple reaction monitoring Methods 0.000 claims description 5
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 3
- 239000005695 Ammonium acetate Substances 0.000 claims description 3
- 229940043376 ammonium acetate Drugs 0.000 claims description 3
- 235000019257 ammonium acetate Nutrition 0.000 claims description 3
- 238000000889 atomisation Methods 0.000 claims description 3
- 239000003480 eluent Substances 0.000 claims description 3
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 3
- 239000012362 glacial acetic acid Substances 0.000 claims description 3
- 239000007921 spray Substances 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 239000011159 matrix material Substances 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 235000015112 vegetable and seed oil Nutrition 0.000 claims description 2
- 239000008158 vegetable oil Substances 0.000 claims description 2
- 238000011020 pilot scale process Methods 0.000 claims 1
- 238000000926 separation method Methods 0.000 abstract description 3
- 238000002156 mixing Methods 0.000 abstract description 2
- KCHSYHMDYRYJIU-UHFFFAOYSA-N C(C)#N.C1(=CC=CC=C1)N=C=S.Cl Chemical compound C(C)#N.C1(=CC=CC=C1)N=C=S.Cl KCHSYHMDYRYJIU-UHFFFAOYSA-N 0.000 abstract 1
- 238000001914 filtration Methods 0.000 abstract 1
- 239000000126 substance Substances 0.000 description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 239000012071 phase Substances 0.000 description 8
- QKFJKGMPGYROCL-UHFFFAOYSA-N phenyl isothiocyanate Chemical compound S=C=NC1=CC=CC=C1 QKFJKGMPGYROCL-UHFFFAOYSA-N 0.000 description 8
- 150000001412 amines Chemical class 0.000 description 6
- 235000019441 ethanol Nutrition 0.000 description 4
- 238000004811 liquid chromatography Methods 0.000 description 4
- 238000001294 liquid chromatography-tandem mass spectrometry Methods 0.000 description 4
- 238000001819 mass spectrum Methods 0.000 description 4
- 229940117953 phenylisothiocyanate Drugs 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000000132 electrospray ionisation Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000002203 pretreatment Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical group N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 241000023320 Luma <angiosperm> Species 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 238000010812 external standard method Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- OSWPMRLSEDHDFF-UHFFFAOYSA-N methyl salicylate Chemical compound COC(=O)C1=CC=CC=C1O OSWPMRLSEDHDFF-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 239000012808 vapor phase Substances 0.000 description 2
- AKABKVXLWWIVIW-UHFFFAOYSA-N 1,1-diisocyanatohexane Chemical compound CCCCCC(N=C=O)N=C=O AKABKVXLWWIVIW-UHFFFAOYSA-N 0.000 description 1
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- YBCVMFKXIKNREZ-UHFFFAOYSA-N acoh acetic acid Chemical compound CC(O)=O.CC(O)=O YBCVMFKXIKNREZ-UHFFFAOYSA-N 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000003005 anticarcinogenic agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 125000001295 dansyl group Chemical group [H]C1=C([H])C(N(C([H])([H])[H])C([H])([H])[H])=C2C([H])=C([H])C([H])=C(C2=C1[H])S(*)(=O)=O 0.000 description 1
- AFZSMODLJJCVPP-UHFFFAOYSA-N dibenzothiazol-2-yl disulfide Chemical compound C1=CC=C2SC(SSC=3SC4=CC=CC=C4N=3)=NC2=C1 AFZSMODLJJCVPP-UHFFFAOYSA-N 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 150000002171 ethylene diamines Chemical class 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000001917 fluorescence detection Methods 0.000 description 1
- 235000011389 fruit/vegetable juice Nutrition 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- ODGAOXROABLFNM-UHFFFAOYSA-N polynoxylin Chemical compound O=C.NC(N)=O ODGAOXROABLFNM-UHFFFAOYSA-N 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010200 validation analysis Methods 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
Landscapes
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
Abstract
The invention discloses method that is a kind of while measuring ethylenediamine, propane diamine and hexamethylene diamine the amount of migration in food contact material and product, feature is to include by food contact material and food simulants by food simulants test solution by migrating experiment acquisition；It takes food simulants test solution to be placed in plastic tube, hydrochloric acid phenyl isothiocyanate acetonitrile solution and triethylamine acetonitrile solution is added, after be vortexed mixing, water-bath the step of centrifugal filtration film；The step of standard curve making；The step of liquid chromatogram separation and Mass Spectrometer Method；Ethylenediamine in sample solution, 1 are finally calculated by standard curve, 2- propane diamine and 1, the concentration of 6- hexamethylene diamine, according to the calculation method of determinand the amount of migration in food contact material and product, obtain ethylenediamine, 1 in food contact material and product, the step of 2- propane diamine and 1, the amount of migration of 6- hexamethylene diamine, advantage are that easy to operate, strong antijamming capability and detection limit are low.
Description
Technical field
The present invention relates to one kind to measure second two in food contact material and product based on liquid chromatography tandem mass spectrometry simultaneously
The method of amine, propane diamine and hexamethylene diamine the amount of migration.
Background technique
Ethylenediamine, 1,2- propane diamine and 1,6- hexamethylene diamine are important industrial chemicals, are widely used in production and living,
It is usually used in producing the daily necessities such as food contact material.In developing food products contact material ethylenediamine, 1,2- propane diamine and 1,6- oneself two
The detection method of amine the amount of migration has important practical significance to guarantee people's food safety.
Ethylenediamine is a kind of colorless and transparent thick liquid, there is ammonia odor, toxic, inflammable, is widely used in manufacture and organises
Close the industries such as object, high-molecular compound, drug, dyestuff and pesticide.The detection method of existing ethylenediamine, mainly vapor phase method and liquid
Xiang Fa.Vapor phase method measurement in ethylenediamine direct injected, detection limit it is minimum arrive 0.02mg/L, but in this method ethylenediamine appearance compared with
Fastly, it is easy to be disturbed.Liquid chromatography for measuring has been reported that ethylenediamine dansyl Cl is derivative, with ultraviolet after liquid chromatogram separation
Detector detection, detection are limited to 0.5mg/L.
1,2- propane diamine is a kind of colourless liquid juice, has strong basicity and strong hygroscopicity, and generation white is contacted with air
Smog.Soluble easily in water, ethyl alcohol and chloroform do not dissolve in ether and benzene.Industrial 1,2- propane diamine is for producing beneficiation reagent, metal
Passivator, aviation resin curing agent, thiofide, for producing the centre of anticarcinogen tetrahydroform in medical industry
Body.1,2- propane diamine detection method is less, and the country is without relevant document report.
1,6- hexamethylene diamine is a kind of strong organic base, flammable, toxic, is corrosive.1,6- hexamethylene diamine is mainly used for synthesizing
Nylon66 fiber and 610 resins, also to synthesis of polyurethane resin, ion exchange resin and hexylidene diisocyanate and as urea
The curing agent of urea formaldehyde, epoxy resin etc., organic crosslinking agent etc..The detection method liquid chromatography of existing 1,6- hexamethylene diamine, has
It reports that hexamethylene diamine is derivative with dansyl Cl, fluorescence detection is used after liquid chromatogram separation, detection is limited to 10 ng/mL.Currently, domestic
It is outer disclose not yet it is any about be based on liquid chromatography tandem mass spectrometry and meanwhile measure ethylenediamine in food contact material and product,
The correlative study of the method for 1,2- propane diamine and 1,6- hexamethylene diamine the amount of migration is reported.
Summary of the invention
Technical problem to be solved by the invention is to provide a kind of easy to operate, strong antijamming capability and detection limit are low
Ethylenediamine in food contact material and product, propane diamine and hexamethylene diamine the amount of migration are measured simultaneously based on liquid chromatography tandem mass spectrometry
Method.
The technical scheme of the invention to solve the technical problem is: a kind of measure food contact material and system simultaneously
The method of ethylenediamine, propane diamine and hexamethylene diamine the amount of migration in product, comprising the following steps:
(1) sample treatment
Food simulants test solution is obtained by food contact material and food simulants by migration experiment；Take food simulants test solution
It is placed in plastic tube, 0.1M hydrochloric acid, 0.1mol/L phenyl isothiocyanate acetonitrile solution and 1mol/L triethylamine acetonitrile solution is added,
It is vortexed and mixes 1min, water-bath 1h at 80 DEG C is centrifuged, excessively 0.22 μm of filter membrane, upper machine sample introduction, wherein food simulants test solution, salt
Acid, phenyl isothiocyanate acetonitrile solution and triethylamine acetonitrile solution volume ratio are 2:98:25:25；
(2) standard curve making
Draw 10 μ g/mL ethylenediamine of concentration, 1,2- propane diamine and 1,6- hexamethylene diamine mixed standard solution, with 0.1M hydrochloric acid constant volume,
It is configured to the mixed standard solution of 100ng/mL, 200ng/mL, 500ng/mL, 1000ng/mL, 2000ng/mL respectively；Take standard
Solution is placed in plastic tube, and 0.1M hydrochloric acid, 0.1mol/L phenyl isothiocyanate acetonitrile solution and 1mol/L triethylamine acetonitrile is added
Solution is vortexed and mixes 1min, water-bath 1h at 80 DEG C, centrifugation, excessively 0.22 μm of filter membrane, upper machine sample introduction, using concentration as abscissa, instrument
Device response is ordinate, does matrix mark-on standard curve, the foundation quantitative as testing concentration in sample treatment solution, wherein
Standard solution, hydrochloric acid, phenyl isothiocyanate acetonitrile solution and triethylamine acetonitrile solution volume ratio be 2:98:25:25, response=
Standard items peak area/standard items quality；
(3) liquid chromatogram separates
Liquid chromatogram flow velocity: 0.300 mL/min；
Mobile phase: A phase is acetonitrile, and B phase is ammonium acetate-acetic acid solution, and eluent gradient elution program is shown in Table 1；
The liquid-phase chromatographic analysis time: 12 min；
Sample volume: 5 μ L；
Chromatographic column temperature: 30 DEG C；
Compound Retention time: ethylenediamine: 5.81 min；1,2- propane diamine: 6.90 min；1,6- hexamethylene diamine: 8.98 min；
1 mobile phase ratio of table
；
(4) Mass Spectrometer Method
Ion source: electric spray ion source (ESI)；
Detection mode: multiple-reaction monitoring (MRM)；
Scanning mode: positive ion mode；
Capillary voltage: positive ion mode, 4000V；
Ion source temperature: 150 DEG C；
Dry gas stream amount: 5L/min；
Atomization gas pressure: 45psi；
Sheath temperature degree: 350 DEG C；Sheath gas (N2) flow: 8L/min；Other mass spectrometry parameters are shown in Table 2；
2. mass spectrometry parameters of table
；
(5) density calculating method
The concentration of ethylenediamine in sample solution, propane diamine and hexamethylene diamine is calculated by standard curve, according to food contact material
And in product determinand the amount of migration calculation method, obtain ethylenediamine in food contact material and product, 1,2- propane diamine and 1,
The amount of migration of 6- hexamethylene diamine.
Food simulants as described in step (1) include the ethyl alcohol of the acetic acid solution of 4% volume fraction, 10% volume fraction
Aqueous solution, the ethanol solution of 20% volume fraction, the ethanol solution of 50% volume fraction, 95% volume fraction ethanol water,
The acetic acid solution and vegetable oil of 4% volume fraction.
Ammonium acetate-acetic acid solutions method is as follows in step (3): 1.54g ammonium acetate being dissolved in 500mL water, is added
10mL glacial acetic acid, is settled to 1000mL.
Step (4) circular is as follows: for using mg/dm2When for unit, the migration of various food simulants test solutions
Measure basisIt calculates, wherein X is determinand ethylenediamine, 1,2- propane diamine or 1, and 6- hexamethylene diamine moves
Shifting amount, unit mg/dm2；C be obtained by migration test in food simulants test solution ethylenediamine, 1,2- propane diamine or 1,6- oneself
The content of diamines, unit are mg/L or mg/kg；C0For ethylenediamine, 1,2- propane diamine and 1,6- in blank food simulants oneself two
The content of amine, unit are mg/L or mg/kg；V is food simulants volume or quality in migration test, and unit is L or kg, described
Blank test solution is the food simulants test solution not contacted with food contact material；S is sample and food simulants in migration test
The area of contact, unit dm2；
When using mg/kg as unit, the amount of migration of various food simulants test solutions according toIt calculates,
In, X1For determinand ethylenediamine, 1,2- propane diamine or 1, the amount of migration of 6- hexamethylene diamine, unit mg/kg；C is migration test
Determinand ethylenediamine, 1,2- propane diamine or 1 in gained food simulants test solution, the content of 6- hexamethylene diamine, unit be mg/L or
mg/kg；C0For ethylenediamine, 1,2- propane diamine or 1 in blank food simulants, the content of 6- hexamethylene diamine, unit be mg/L or
mg/kg；V is food simulants volume or quality in migration test, and unit is L or kg；S is sample and food mould in migration test
The area of quasi- object contact, unit dm2；F is the contact area S of food contact material and product and contacts the ratio S/ of food quality
V, unit dm2/ kg or dm2/L。
Compared with the prior art, the advantages of the present invention are as follows: present invention firstly discloses one kind to be based on liquid chromatography tandem
Mass spectrography measures ethylenediamine in food contact material and product, 1,2- propane diamine and 1 simultaneously, the method for 6- hexamethylene diamine the amount of migration,
In the presence of triethylamine, ethylenediamine, 1,2- propane diamine, 1,6- hexamethylene diamine are reacted with phenyl isothiocyanate, and generating one kind can be
The substance of ion is generated in electrospray ionization source mass spectrum (source ESI), which separates by liquid chromatogram, is examined with electrospray ionization source mass spectrum
It surveys, quantified by external standard method, this method can effectively solve the content of accurate detection ethylenediamine, 1,2- propane diamine, 1,6- hexamethylene diamine, have
Advantage easy to operate, method is stable, strong antijamming capability and detection limit are low.
Detailed description of the invention
Fig. 1 is ethylenediamine, 1,2- propane diamine and 1,6- hexamethylene diamine 10ng/mL chromatogram.
Specific embodiment
The present invention will be described in further detail below with reference to the embodiments of the drawings.
Specific embodiment
1, preparation of reagents and instrument
0.1 mol/L phenyl isothiocyanate acetonitrile solution: weighing 1.35g phenyl isothiocyanate, is settled to 100mL with acetonitrile.
1 mol/L triethylamine acetonitrile solution: 10.1g triethylamine is weighed, is settled to 100mL with acetonitrile.
0.1M hydrochloric acid: 0.86mL concentrated hydrochloric acid is taken to be dissolved in 100mL volumetric flask.
10 μ g/mL ethylenediamines, 1,2- propane diamine and 1,6- hexamethylene diamine mixed standard solution preparation: 100 μ L 1mg/ are respectively taken
ML ethylenediamine, 1mg/mL 1,2- propane diamine and 1mg/mL 1 are settled to 10mL with acetonitrile after the mixing of 6- hexamethylene diamine standard solution,
Wherein 1mg/mL ethylenediamine standard solution is prepared: being weighed 10 mg ethylenediamine standard substances, is settled to 10 mL with acetonitrile；1mg/
ML1,2- propane diamine standard solution are prepared: weighing 10 mg1,2- propane diamine standard substance is settled to 10 mL with acetonitrile；1mg/
ML1,6- hexamethylene diamine standard solution are prepared: weighing 10 mg1,6- hexamethylene diamine standard substance is settled to 10 mL with acetonitrile；Second two
The purity of amine, 1,6- hexamethylene diamine and 1,2- propane diamine standard items is all larger than 99%.
Instrument: liquid chromatography mass combined instrument: Agilent1290 liquid chromatogram, chromatographic column: Phenomenex Luma
C18(150mm × 2mm, 3 μm) or suitable person；6460 mass spectrograph of Agilent.
2, the side of ethylenediamine in food contact material and product, 1,2- propane diamine and 1,6- hexamethylene diamine the amount of migration is measured simultaneously
Method, testing principle: in the presence of triethylamine, ethylenediamine, 1,2- propane diamine, 1,6- hexamethylene diamine are reacted with phenyl isothiocyanate,
The substance of ion can be generated in electrospray ionization source mass spectrum (source ESI) by generating one kind, which separates by liquid chromatogram, electricity consumption
Spraying source Mass Spectrometer Method, quantified by external standard method.Specific step is as follows:
(1) sample treatment
Food simulants test solution is obtained by food contact material and food simulants by migration experiment, including aqueous-based food simulation
(food simulants test solution is according to the requirement of GB31604.1 and GB5006.156 from moving for object test solution and oil-based foods analogies test solution
It obtains, should be protected from light stored refrigerated in refrigerator in shift test)；20 μ L of food simulants test solution is taken, is placed in 15mL plastic tube, adds
Enter 980 μ L of 0.1M hydrochloric acid, 250 μ L and 1mol/L triethylamine acetonitrile solution of 0.1mol/L phenyl isothiocyanate acetonitrile solution, 250 μ L,
It is vortexed and mixes 1min, water-bath 1h at 80 DEG C, 0.22 μm of filter membrane, upper machine sample introduction are crossed in centrifugation；
(2) standard curve making
Draw 10 μ g/mL ethylenediamine of concentration, 1,2- propane diamine and 1,6- hexamethylene diamine mixed standard solution, with 0.1M hydrochloric acid constant volume,
It is configured to the mixed standard solution of 100ng/mL, 200ng/mL, 500ng/mL, 1000ng/mL, 2000ng/mL respectively；Take standard
20 μ L of solution, is placed in 15mL plastic tube, and 980 μ L of 0.1M hydrochloric acid, 250 μ of 0.1mol/L phenyl isothiocyanate acetonitrile solution is added
250 μ L of L and 1mol/L triethylamine acetonitrile solution is vortexed and mixes 1min, water-bath 1h at 80 DEG C, and 0.22 μm of filter membrane is crossed in centrifugation, on
Machine sample introduction, using concentration as abscissa, instrumental response value (response=standard items peak area/standard items quality) is ordinate, does base
Matter mark-on standard curve, the foundation quantitative as testing concentration in sample treatment solution；
(3) liquid chromatogram separates
Chromatographic column: Phenomenex Luma C18(150mm × 2mm, 3 μm) or suitable person；
Liquid chromatogram flow velocity: 0.300 mL/min；
Mobile phase: A phase is acetonitrile, and B phase is ammonium acetate-acetic acid solution, and eluent gradient elution program is shown in Table 1；Ammonium acetate-acetic acid
The following 1.54g ammonium acetate of solution preparation method is dissolved in 500mL water, and 10mL glacial acetic acid is added, is settled to 1000mL；
The liquid-phase chromatographic analysis time: 12 min；
Sample volume: 5 μ L；
Chromatographic column temperature: 30 DEG C；
As shown in Figure 1, Compound Retention time: ethylenediamine: 5.81 min；1,2- propane diamine: 6.90 min；1,6- hexamethylene diamine:
8.98 min；
1 mobile phase ratio of table
；
(4) Mass Spectrometer Method
Ion source: electric spray ion source (ESI)；
Detection mode: multiple-reaction monitoring (MRM)；
Scanning mode: positive ion mode；
Capillary voltage: positive ion mode, 4000V；
Ion source temperature: 150 DEG C；
Dry gas stream amount: 5L/min；
Atomization gas pressure: 45psi；
Sheath temperature degree: 350 DEG C；Sheath gas (N2) flow: 8L/min；Other mass spectrometry parameters are shown in Table 2；
2. mass spectrometry parameters of table
；
(5) density calculating method
Ethylenediamine in sample solution, 1,2- propane diamine and 1, the concentration of 6- hexamethylene diamine, according to food are calculated by standard curve
The calculation method (being calculated according to GB5009.156) of determinand the amount of migration in contact material and product obtains food contact material
The amount of migration of ethylenediamine, 1,2- propane diamine and 1,6- hexamethylene diamine in material and product.Circular is as follows: for using mg/dm2
When for unit, the amount of migration of various food simulants test solutions according toIt calculates, wherein X is determinand second
Diamines, 1,2- propane diamine or 1, the amount of migration of 6- hexamethylene diamine, unit mg/dm2；C is food simulants obtained by migration test
Ethylenediamine, 1,2- propane diamine or 1 in test solution, the content of 6- hexamethylene diamine, unit are mg/L or mg/kg；C0For blank food mould
Ethylenediamine, 1,2- propane diamine and 1 in quasi- object, the content of 6- hexamethylene diamine, unit are mg/L or mg/kg；V is food in migration test
Analogies volume or quality, unit are L or kg, and the blank test solution is the food simulants examination not contacted with food contact material
Liquid；S is the area that sample is contacted with food simulants in migration test, unit dm2；
When using mg/kg as unit, the amount of migration of various food simulants test solutions according toIt calculates,
In, X1For determinand ethylenediamine, 1,2- propane diamine or 1, the amount of migration of 6- hexamethylene diamine, unit mg/kg；C is migration test
Determinand ethylenediamine, 1,2- propane diamine or 1 in gained food simulants test solution, the content of 6- hexamethylene diamine, unit be mg/L or
mg/kg；C0For ethylenediamine, 1,2- propane diamine or 1 in blank food simulants, the content of 6- hexamethylene diamine, unit be mg/L or
mg/kg；V is food simulants volume or quality in migration test, and unit is L or kg；S is sample and food mould in migration test
The area of quasi- object contact, unit dm2；F is the contact area S of food contact material and product and contacts the ratio S/ of food quality
V, unit dm2/ kg or dm2/L。
3, method validation is tested
3.1 detection limit
After ethylenediamine, 1,2- propane diamine, 1,6- hexamethylene diamine standard items are diluted step by step, 20 μ L are taken, are placed in 15mL plastic tube,
980 μ L of 0.1M hydrochloric acid, 250 μ L and 1mol/L triethylamine acetonitrile solution of 0.1mol/L phenyl isothiocyanate acetonitrile solution, 250 μ is added
L is vortexed and mixes 1min, water-bath 1h at 80 DEG C, and 0.22 μm of filter membrane is crossed in centrifugation, and upper machine sample introduction is measured, and obtains three kinds of substances
Detection limit.As a result are as follows: 25 ng/mL of ethylenediamine；25 ng/mL of 1,2- propane diamine；25 ng/mL of 1,6- hexamethylene diamine.
3.2 standard curve ranges:
Ethylenediamine, 1,2- propane diamine and 1,6- hexamethylene diamine standard curve are made, sample is pressed above-mentioned 3.1 method and carried out on after pre-treatment
Machine sample introduction is measured, and obtains the standard curve range of three kinds of substances.
The ethylenediamine range of linearity: 0.05~10 μ g/mL, linear correlation R2>0.99；
1, the 2- propane diamine range of linearity: 0.05~10 μ g/mL, linear correlation R2>0.99；
1, the 6- hexamethylene diamine range of linearity: 0.05~10 μ g/mL, linear correlation R2>0.99；
3.3 method precisions and the rate of recovery
6 parts of samples that ethylenediamine, 1,2- propane diamine, 1,6- hexamethylene diamine standard concentration are 500 ng/mL will be contained respectively, pressed
After above-mentioned 3.1 method carries out pre-treatment, upper machine sample introduction is measured, and obtains the essence using three kinds of substances in this method measurement water sample
Density the results are shown in Table 3.
Table 3 measures the precision of ethylenediamine, 1,2- propane diamine, 1,6- hexamethylene diamine in water sample
；
It is equal ethylenediamine, 1,2- propane diamine, 1,6- hexamethylene diamine standard concentration will to be added in varieties of food items analogies sample respectively
For 500 ng/mL, after carrying out pre-treatment by above-mentioned 3.1 method, upper machine sample introduction is measured, and is obtained and is measured water sample using this method
In three kinds of substances the rate of recovery, the results are shown in Table 4.
Table 4 measures the rate of recovery of ethylenediamine, 1,2- propane diamine, 1,6- hexamethylene diamine in water sample
By above-mentioned table 3 and table 4 it is found that the present invention establish based on liquid chromatography tandem mass spectrometry and meanwhile measure food contact material
And the method for ethylenediamine, 1,2- propane diamine and 1,6- hexamethylene diamine the amount of migration has good precision and the rate of recovery in product.
3.4 method advantages:
Method anti-interference ability: this method is detected using triple quadrupole bar mass spectrum, while being able to detect three kinds of substances, and
Strong antijamming capability, two replace organic amine and phenyl isothiocyanate equation as follows,
。
Above description is not limitation of the present invention, and the present invention is also not limited to the example above.The art it is common
Within the essential scope of the present invention, the variations, modifications, additions or substitutions made also should belong to protection of the invention to technical staff
Range.
Claims (6)
1. a kind of method for measuring ethylenediamine, propane diamine and hexamethylene diamine the amount of migration in food contact material and product simultaneously, special
Sign be the following steps are included:
(1) sample treatment
Food simulants test solution is obtained by food contact material and food simulants by migration experiment；Take food simulants test solution
It is placed in plastic tube, 0.1M hydrochloric acid, 0.1mol/L phenyl isothiocyanate acetonitrile solution and 1mol/L triethylamine acetonitrile solution is added,
It is vortexed and mixes 1min, water-bath 1h at 80 DEG C is centrifuged, excessively 0.22 μm of filter membrane, upper machine sample introduction, wherein food simulants test solution, salt
Acid, phenyl isothiocyanate acetonitrile solution and triethylamine acetonitrile solution volume ratio are 2:98:25:25；
(2) standard curve making
Draw 10 μ g/mL ethylenediamine of concentration, 1,2- propane diamine and 1,6- hexamethylene diamine mixed standard solution, with 0.1M hydrochloric acid constant volume,
It is configured to the mixed standard solution of 100ng/mL, 200ng/mL, 500ng/mL, 1000ng/mL, 2000ng/mL respectively；Take standard
Solution is placed in plastic tube, and 0.1M hydrochloric acid, 0.1mol/L phenyl isothiocyanate acetonitrile solution and 1mol/L triethylamine acetonitrile is added
Solution is vortexed and mixes 1min, water-bath 1h at 80 DEG C, centrifugation, excessively 0.22 μm of filter membrane, upper machine sample introduction, using concentration as abscissa, instrument
Device response is ordinate, does matrix mark-on standard curve, the foundation quantitative as testing concentration in sample treatment solution, wherein
Standard solution, hydrochloric acid, phenyl isothiocyanate acetonitrile solution and triethylamine acetonitrile solution volume ratio be 2:98:25:25, response=
Standard items peak area/standard items quality；
(3) liquid chromatogram separates
Mobile phase: A phase is acetonitrile, and B phase is ammonium acetate-acetic acid solution, liquid chromatogram flow velocity: 0.300 mL/min；Sample volume: 5
μL；Chromatographic column temperature: 30 DEG C；
(4) Mass Spectrometer Method
Ion source: electric spray ion source；Detection mode: multiple-reaction monitoring；Capillary voltage: positive ion mode, 4000V；Ion
Source temperature: 150 DEG C；Dry gas stream amount: 5L/min；Atomization gas pressure: 45psi；Sheath temperature degree: 350 DEG C；Sheath throughput: 8L/
min；；
(5) density calculating method
Ethylenediamine in sample solution, 1,2- propane diamine and 1, the concentration of 6- hexamethylene diamine, according to food are calculated by standard curve
The calculation method of determinand the amount of migration in contact material and product obtains ethylenediamine in food contact material and product, 1,2- third
The amount of migration of diamines and 1,6- hexamethylene diamine.
2. according to claim 1 while measuring ethylenediamine, propane diamine and hexamethylene diamine in food contact material and product and move
The method of shifting amount, it is characterised in that: food simulants as described in step (1) include the acetic acid solution of 4% volume fraction, 10%
The ethanol water of volume fraction, the ethanol solution of 20% volume fraction, the ethanol solution of 50% volume fraction, 95% volume point
The acetic acid solution and vegetable oil of several ethanol water, 4% volume fraction.
3. according to claim 1 while measuring ethylenediamine, propane diamine and hexamethylene diamine in food contact material and product and move
The method of shifting amount, it is characterised in that ammonium acetate-acetic acid solutions method is as follows in step (3): 1.54g ammonium acetate is dissolved in
In 500mL water, 10mL glacial acetic acid is added, is settled to 1000mL.
4. according to claim 1 while measuring ethylenediamine, propane diamine and hexamethylene diamine in food contact material and product and move
The method of shifting amount, it is characterised in that eluent gradient elution program is shown in Table 1 in step (3):
1 mobile phase ratio of table
。
5. according to claim 1 while measuring ethylenediamine, propane diamine and hexamethylene diamine in food contact material and product and move
The method of shifting amount, it is characterised in that remaining mass spectrometry parameters is shown in Table 2 in step (4):
2. mass spectrometry parameters of table
。
6. according to claim 1 while measuring ethylenediamine, propane diamine and hexamethylene diamine in food contact material and product and move
The method of shifting amount, it is characterised in that step (5) circular is as follows: for using mg/dm2When for unit, various food moulds
The amount of migration of quasi- object test solution according toCalculate, wherein X be determinand ethylenediamine, 1,2- propane diamine or
The amount of migration of 1,6- hexamethylene diamine, unit mg/dm2；C is ethylenediamine, 1,2- third in food simulants test solution obtained by migration test
Diamines or 1, the content of 6- hexamethylene diamine, unit are mg/L or mg/kg；C0For ethylenediamine, 1,2- third in blank food simulants
Diamines and 1, the content of 6- hexamethylene diamine, unit are mg/L or mg/kg；V is food simulants volume or quality in migration test, single
Position is L or kg, and the blank test solution is the food simulants test solution not contacted with food contact material；S is migration test pilot scale
The area that sample is contacted with food simulants, unit dm2；
When using mg/kg as unit, the amount of migration of various food simulants test solutions according toIt calculates,
In, X1 is determinand ethylenediamine, 1,2- propane diamine or 1, the amount of migration of 6- hexamethylene diamine, unit mg/kg；C is migration test
Determinand ethylenediamine, 1,2- propane diamine or 1 in gained food simulants test solution, the content of 6- hexamethylene diamine, unit be mg/L or
mg/kg；C0For ethylenediamine, 1,2- propane diamine or 1 in blank food simulants, the content of 6- hexamethylene diamine, unit be mg/L or
mg/kg；V is food simulants volume or quality in migration test, and unit is L or kg；S is sample and food mould in migration test
The area of quasi- object contact, unit dm2；F is the contact area S of food contact material and product and contacts the ratio S/ of food quality
V, unit dm2/ kg or dm2/L。
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| CN111879861B (en) * | 2020-04-03 | 2021-09-28 | 江南大学 | Method for accurately detecting content of hexamethylene diamine in fermentation liquor |
| CN116660398A (en) * | 2023-03-31 | 2023-08-29 | 南京海关危险货物与包装检测中心 | Food contact material and method for detecting migration quantity of N-ethyl o-toluenesulfonamide in product |
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| CN116973343A (en) * | 2023-07-04 | 2023-10-31 | 岭南师范学院 | Method for detecting hexamethylenediamine |
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