CN112881568B - Method for simultaneously measuring multiple associated harmful substances in food thermal processing - Google Patents
Method for simultaneously measuring multiple associated harmful substances in food thermal processing Download PDFInfo
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- 239000000126 substance Substances 0.000 title claims abstract description 69
- 235000013305 food Nutrition 0.000 title claims abstract description 27
- 238000000034 method Methods 0.000 title claims abstract description 20
- 238000012545 processing Methods 0.000 title claims abstract description 14
- 238000001514 detection method Methods 0.000 claims abstract description 28
- 235000021067 refined food Nutrition 0.000 claims abstract description 10
- AIFRHYZBTHREPW-UHFFFAOYSA-N β-carboline Chemical compound N1=CC=C2C3=CC=CC=C3NC2=C1 AIFRHYZBTHREPW-UHFFFAOYSA-N 0.000 claims description 28
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 27
- DVCCCQNKIYNAKB-UHFFFAOYSA-N MeIQx Chemical compound C12=NC(C)=CN=C2C=CC2=C1N=C(N)N2C DVCCCQNKIYNAKB-UHFFFAOYSA-N 0.000 claims description 26
- 239000000243 solution Substances 0.000 claims description 25
- GMGWMIJIGUYNAY-UHFFFAOYSA-N MeIQ Chemical compound CC1=CC2=NC=CC=C2C2=C1N(C)C(N)=N2 GMGWMIJIGUYNAY-UHFFFAOYSA-N 0.000 claims description 22
- 239000012224 working solution Substances 0.000 claims description 15
- LOUPRKONTZGTKE-WZBLMQSHSA-N Quinine Chemical compound C([C@H]([C@H](C1)C=C)C2)C[N@@]1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OC)C=C21 LOUPRKONTZGTKE-WZBLMQSHSA-N 0.000 claims description 14
- ARZWATDYIYAUTA-UHFFFAOYSA-N 3-methyl-3H-imidazo[4,5-f]quinolin-2-amine Chemical compound C1=CC2=NC=CC=C2C2=C1N(C)C(N)=N2 ARZWATDYIYAUTA-UHFFFAOYSA-N 0.000 claims description 12
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 12
- 238000010828 elution Methods 0.000 claims description 12
- HKZZYGFWIFKKIR-UHFFFAOYSA-N 3-Methyl-3H-imidazo[4,5-f]quinoxalin-2-amine Chemical compound C1=CC2=NC=CN=C2C2=C1N(C)C(N)=N2 HKZZYGFWIFKKIR-UHFFFAOYSA-N 0.000 claims description 11
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 11
- 238000001195 ultra high performance liquid chromatography Methods 0.000 claims description 11
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- GWMHBZDOVFZVQC-UHFFFAOYSA-N 1,5,6-trimethylimidazo[4,5-b]pyridin-2-amine Chemical compound N1=C(C)C(C)=CC2=C1N=C(N)N2C GWMHBZDOVFZVQC-UHFFFAOYSA-N 0.000 claims description 9
- 208000002180 Laurin-Sandrow syndrome Diseases 0.000 claims description 9
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 8
- XSCHRSMBECNVNS-UHFFFAOYSA-N quinoxaline Chemical compound N1=CC=NC2=CC=CC=C21 XSCHRSMBECNVNS-UHFFFAOYSA-N 0.000 claims description 8
- NEOGGGHDLGYATP-UHFFFAOYSA-N 1,6-dimethylimidazo[4,5-b]pyridin-2-amine Chemical compound CC1=CN=C2N=C(N)N(C)C2=C1 NEOGGGHDLGYATP-UHFFFAOYSA-N 0.000 claims description 7
- 235000001258 Cinchona calisaya Nutrition 0.000 claims description 7
- UQVKZNNCIHJZLS-UHFFFAOYSA-N PhIP Chemical compound C1=C2N(C)C(N)=NC2=NC=C1C1=CC=CC=C1 UQVKZNNCIHJZLS-UHFFFAOYSA-N 0.000 claims description 7
- LOUPRKONTZGTKE-UHFFFAOYSA-N cinchonine Natural products C1C(C(C2)C=C)CCN2C1C(O)C1=CC=NC2=CC=C(OC)C=C21 LOUPRKONTZGTKE-UHFFFAOYSA-N 0.000 claims description 7
- 238000002347 injection Methods 0.000 claims description 7
- 239000007924 injection Substances 0.000 claims description 7
- 230000014759 maintenance of location Effects 0.000 claims description 7
- 239000011159 matrix material Substances 0.000 claims description 7
- 229960000948 quinine Drugs 0.000 claims description 7
- DCFOWWLJXYYXQG-UHFFFAOYSA-N 1-methyl-4,9-dihydro-3H-pyrido[3,4-b]indole 1-methyl-9H-pyrido[3,4-b]indole Chemical compound N1C2=CC=CC=C2C2=C1C(C)=NCC2.C12=CC=CC=C2NC2=C1C=CN=C2C DCFOWWLJXYYXQG-UHFFFAOYSA-N 0.000 claims description 6
- IQBHNZHUIYORFY-JMUYHTKKSA-N NC1(N(C2(C(=C3N=C(C=NC3=CC2C)C)N1[2H])[2H])C)[2H] Chemical compound NC1(N(C2(C(=C3N=C(C=NC3=CC2C)C)N1[2H])[2H])C)[2H] IQBHNZHUIYORFY-JMUYHTKKSA-N 0.000 claims description 6
- XBJFCYDKBDVADW-UHFFFAOYSA-N acetonitrile;formic acid Chemical group CC#N.OC=O XBJFCYDKBDVADW-UHFFFAOYSA-N 0.000 claims description 6
- 239000006185 dispersion Substances 0.000 claims description 6
- HQVFCQRVQFYGRJ-UHFFFAOYSA-N formic acid;hydrate Chemical compound O.OC=O HQVFCQRVQFYGRJ-UHFFFAOYSA-N 0.000 claims description 6
- 238000004949 mass spectrometry Methods 0.000 claims description 6
- 238000004364 calculation method Methods 0.000 claims description 5
- 238000001819 mass spectrum Methods 0.000 claims description 5
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- 239000003643 water by type Substances 0.000 claims description 5
- VQWMRFGOLQDJSV-UHFFFAOYSA-N 3,7,8-trimethylimidazo[4,5-f]quinolin-2-amine Chemical compound C1=C2N=C(C)C(C)=CC2=C2N=C(N)N(C)C2=C1 VQWMRFGOLQDJSV-UHFFFAOYSA-N 0.000 claims description 4
- 238000012417 linear regression Methods 0.000 claims description 4
- 239000011780 sodium chloride Substances 0.000 claims description 4
- 238000011895 specific detection Methods 0.000 claims description 4
- 229940054967 vanquish Drugs 0.000 claims description 4
- HRPVXLWXLXDGHG-FUDHJZNOSA-N 2,3,3-trideuterioprop-2-enamide Chemical compound [2H]C([2H])=C([2H])C(N)=O HRPVXLWXLXDGHG-FUDHJZNOSA-N 0.000 claims description 3
- PBCJIPOGFJYBJE-UHFFFAOYSA-N acetonitrile;hydrate Chemical compound O.CC#N PBCJIPOGFJYBJE-UHFFFAOYSA-N 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
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- 241000607479 Yersinia pestis Species 0.000 claims description 2
- 238000004587 chromatography analysis Methods 0.000 claims description 2
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- 238000012544 monitoring process Methods 0.000 abstract description 3
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- 150000002500 ions Chemical class 0.000 description 9
- 239000000356 contaminant Substances 0.000 description 4
- PSFDQSOCUJVVGF-UHFFFAOYSA-N harman Chemical compound C12=CC=CC=C2NC2=C1C=CN=C2C PSFDQSOCUJVVGF-UHFFFAOYSA-N 0.000 description 4
- IVLCGFRPPGNALI-UHFFFAOYSA-N 2-Amino-3-methyl-9H-pyrido[2,3-b]indole Chemical compound N1C2=CC=CC=C2C2=C1N=C(N)C(C)=C2 IVLCGFRPPGNALI-UHFFFAOYSA-N 0.000 description 3
- JFQHIQJNQCWLNR-UHFFFAOYSA-N 3,7,8-trimethylimidazo[4,5-f]quinoxalin-2-amine Chemical compound C1=C2N(C)C(N)=NC2=C2N=C(C)C(C)=NC2=C1 JFQHIQJNQCWLNR-UHFFFAOYSA-N 0.000 description 3
- CFEPPLAUXZCOJL-UHFFFAOYSA-N 3,8-dimethylimidazo[4,5-f]quinolin-2-amine Chemical compound C12=CC(C)=CN=C2C=CC2=C1N=C(N)N2C CFEPPLAUXZCOJL-UHFFFAOYSA-N 0.000 description 3
- OAPVIBHQRYFYSE-UHFFFAOYSA-N 5-Phenyl-2-pyridinamine Chemical compound C1=NC(N)=CC=C1C1=CC=CC=C1 OAPVIBHQRYFYSE-UHFFFAOYSA-N 0.000 description 3
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 238000004896 high resolution mass spectrometry Methods 0.000 description 3
- HRPVXLWXLXDGHG-DYCDLGHISA-N n-deuterioprop-2-enamide Chemical compound [2H]NC(=O)C=C HRPVXLWXLXDGHG-DYCDLGHISA-N 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- FJTNLJLPLJDTRM-UHFFFAOYSA-N 2-Amino-9H-pyrido[2,3-b]indole Chemical compound C1=CC=C2C3=CC=C(N)N=C3NC2=C1 FJTNLJLPLJDTRM-UHFFFAOYSA-N 0.000 description 2
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000003556 assay Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000002552 multiple reaction monitoring Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000011002 quantification Methods 0.000 description 2
- -1 2-amino-3, 6-dimethylimidazo [4,5-b ] quinoxaline Chemical compound 0.000 description 1
- 239000012491 analyte Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000010411 cooking Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
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- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 231100000024 genotoxic Toxicity 0.000 description 1
- 230000001738 genotoxic effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000000589 high-performance liquid chromatography-mass spectrometry Methods 0.000 description 1
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 description 1
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 description 1
- 125000003473 lipid group Chemical group 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 description 1
- 238000001294 liquid chromatography-tandem mass spectrometry Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
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- 239000000758 substrate Substances 0.000 description 1
- 238000005303 weighing 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
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
-
- 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
- G01N30/88—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86
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- 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 provides a method for simultaneously determining harmful substances in food thermal processing, which comprises the following steps: preparing a harmful substance detection sample to be detected; respectively measuring a standard sample and a to-be-measured harmful substance detection sample to obtain the standard sample, an internal standard of the to-be-measured harmful substance detection sample and a component peak area of the to-be-measured harmful substance detection sample; and calculating a standard curve of the obtained harmful substances to obtain the content of the harmful substances to be detected in the thermally processed food. The invention can realize one-step rapid detection of the content of various harmful substances in food, intuitively reflect the distribution situation of the harmful substances in different thermally processed foods, accurately match and meet quantitative requirements, provide very powerful qualitative evidence and provide a simpler, more convenient and more efficient method for food quality monitoring and evaluation.
Description
Technical Field
The invention relates to the technical field of detection of harmful substances in food processing, in particular to a method for simultaneously measuring various associated harmful substances in food thermal processing by utilizing a hydrophilic chromatographic column.
Background
The food is easy to produce harmful substances such as acrylamide, 5-hydroxymethylfurfural, heterocyclic aromatic amine and the like through Maillard reaction and the like in the hot processing process. All three types of pests have the risk of causing diseases in the human body during cooking, and should be minimized during food processing. It is of great value to evaluate multiple classes of contaminants simultaneously, especially contaminants produced in similar substrates or similar sources representing a common exposure. Assessing the safety risk of contaminants in heat treated foods is of great importance to food safety issues and trade.
A number of assays have been developed in the art to detect a variety of genotoxic compounds during different heat treatments. However, the sensitivity of the liquid chromatography detection method is low, and the accuracy of the conventional high performance liquid chromatography-tandem mass spectrometry technology is also poor. Furthermore, separate extraction methods will take a lot of time and costs and simultaneous extraction of substances with large polarity differences will inevitably require cumbersome sample handling, especially lipid residues in certain high fat samples may affect mass spectrometry detection. Therefore, the development of simultaneous extraction and detection of multiple contaminants at once is very important for thoroughly cleaning the features of thermally processed foods.
Disclosure of Invention
The invention provides a method for measuring harmful substances such as acrylamide, 5-hydroxymethylfurfural and 14 heterocyclic aromatic amines in thermally processed foods based on an ultra-high performance liquid chromatography high-resolution mass spectrometry technology, so as to realize accurate monitoring and quantification of the harmful compounds in the thermally processed foods.
In order to achieve the above object, the present invention provides a method for simultaneously measuring harmful substances in food thermal processing, comprising the steps of:
s1, adding a sample to be detected into a mixed internal standard working solution according to a ratio of 15-20:1 (m/v), and then, according to a ratio of 1:100 (v/v) adding the mixture to an aqueous acetonitrile solution with a volume fraction of 50%, homogenizing at a rotation speed of 1000-15000rpm to obtain a food matrix dispersion;
s2, taking the food matrix dispersion liquid, and adding an n-hexane solution and anhydrous MgSO (MgSO) according to the ratio of 10:8:1 (v/m/m) 4 Shaking and mixing with NaCl, centrifuging at 1000-4000g, and collecting middle layer liquid to obtain sample to be volatilized;
s3, taking the sample to be volatilized, drying, then redissolving the sample with an acetonitrile aqueous solution with the volume fraction of 50%, centrifuging at a high speed of 10000-20000g, and taking a supernatant to obtain a harmful substance detection sample to be detected;
s4, sample measurement: respectively measuring a standard sample and the to-be-detected harmful substance detection sample prepared in the step S3 to obtain an internal standard of the standard sample and the to-be-detected harmful substance detection sample and a component peak area of the to-be-detected harmful substance detection sample;
s5, performing linear regression according to the retention time of the standard sample and the ratio of the concentration of the standard sample to the peak area of the harmful substance to be detected to the sample component and the internal standard peak area to obtain a harmful substance standard curve; and (3) taking the ratio of the to-be-detected component of the to-be-detected harmful substance detection sample obtained in the step (S3) to the internal standard peak area into a standard curve for calculation, and thus obtaining the content of the to-be-detected harmful substance in the thermally processed food.
Preferably, the assay method in step S4 is performed by ultra-high performance liquid chromatography and mixed quadrupole-rail mass spectrometry using a Waters HSS T3 (2.1 mm×100mm,1.8 μm) hydrophilic chromatography column.
Preferably, specific detection conditions are:
sample injection amount: 1 μl; acquisition mode: full ms+prm;
mobile phase: phase a is 0.1% formic acid-water solution by volume fraction; phase B is formic acid-acetonitrile solution with volume fraction of 0.1%;
elution flow rate: 0.3mL/min;
elution gradient: 1% B,0min;1% B,0-1.5min;99% B,1.5-16.5min;1% B,16.6-20.0min.
Preferably, the preparation method of the mixed internal standard working solution in step S1 includes: acrylamide-d is selected 3 And 2-amino-3, 4, 8-trimethylimidazo [4,5-f]Quinoxaline-d 3 (4,8-DiMeIQx-d 3 ) As internal standard, mixed internal standard working solution with the final concentration of 1-2 mug/mL is prepared respectively.
Preferably, the drying method in step S3 is as follows: nitrogen drying at room temperature until the liquid had evaporated.
Preferably, the preparation method of the standard sample in step S4 is as follows: acrylamide, 5-hydroxymethylfurfural, 2-amino-1, 6-dimethylimidazo [4,5-b ] pyridine (DMIP), 2-amino-1, 5, 6-trimethylimidazo [4,5-b ] pyridine (1, 5, 6-TMIP), 2-amino-1-methyl-6-phenylimidazo [4,5-b ] pyridine (PhIP), 2-amino-3-methylimidazo [4,5-f ] quinoline (IQ), 2-amino-1-methylimidazo [4,5-b ] quinine (IQ [4,5-b ]), 2-amino-3, 4-dimethylimidazo [4,5-f ] quinoline (MeIQ), 2-amino-3-methylimidazo [4,5-f ] quinoxaline (IQx), 2-amino-3, 8-dimethylimidazo [4,5-f ] quinoxaline (8-MeIQx), 2-amino-3, 7, 8-trimethylimidazo [4,5-f ] quinoline (IQ), 2-amino-3, 5-f ] quinoxaline (MeIQx), 2-amino-3, 5-f ] quinoline (MeIQ) and 2-amino-3-methylimidazo [4,5-f ] quinoxaline (MeIQ), 9H-pyrido [3,4-b ] indole (Norharman) and 1-methyl-9H-pyrido [3,4-b ] indole (Harman) are used as standard substances to prepare working solutions with concentrations of 0.10,1.00,10.00,20.00,50.00,100.00,200.00 and 500.00ng/mL respectively, wherein the final concentration of an internal standard in each concentration standard substance is 100-200ng/mL.
Preferably, the calculating method of the content of the harmful substance to be detected in step S5 is as follows:
standard curve of object to be measured: y=ax+b
Y=peak area of component to be measured/peak area of internal standard
X=content of harmful substance to be measured
The invention has the beneficial effects that:
1. the invention carries out quantitative research based on the ultra-high performance liquid chromatography high resolution mass spectrometry technology so as to reduce the matrix effect and the complexity of the analyte in the detection process. In the unique mass spectrometry signal acquisition mode of Full ms+prm, the quadrupole mass filter transmits only defined ions in the inclusion list to the intermediate C-trap, preparing for sample injection to more efficient high energy collision dissociation (HCD), and then performing high concentration analysis resolution in an Orbitrap analyzer. The C trap trapping part of the Q exact HF-X mass spectrometer replaces the final quadrupole rod part of the triple quadrupole rod instrument, and the transmission of ion products in the whole mass range can be completed. Q exact HF-X mass spectrometers can provide accurate mass to charge ratio scans, five bits after the decimal point, which is not possible with other LC-MS and HPLC-MS. In the quantitative determination of high fat content food samples, complete mass spectrum information is obtained by Q exact HF-X, including complete ion information obtained by full spectrum scanning, rather than ion pair spectrum information obtained by conventional triple quadrupole Multiple Reaction Monitoring (MRM). This allows the mass spectrum obtained when the sample is measured to have many ion fragments in line with each other in the standard, in addition to the precursor ion and product ion information present in pairs, and this exact match not only meets the quantitative requirements, but also provides very strong qualitative evidence.
2. The invention adopts Waters HSS T3 chromatographic column to tolerate water phase with the highest proportion of 100%, which can make the object to be detected with larger polarity obtain better chromatographic peak shape. The Full ms+prm signal acquisition mode in the mass spectrometer Q-actual HF is a mode in which HCD cell collision and scanning is performed on precursor ions contained in the list immediately after all ion scans that do not pass through the quaternary rod. Its performance is largely dependent on the combination of high performance quadrupole precursor selection and high resolution and accurate mass Orbitrap detection, so it exhibits the same or even better quantitative applicability as a triple quadrupole-based mass spectrometer, can provide high resolution in short analysis times, and allows simultaneous detection and quantification of large amounts of compounds.
3. The method for measuring 14 heterocyclic aromatic amines such as acrylamide, 5-hydroxymethylfurfural and the like in the thermally processed food by using the ultra-high performance liquid chromatography and high resolution mass spectrometry can realize one-step rapid detection of the content of various harmful substances in the food, intuitively reflect the distribution situation of the harmful substances in different thermally processed foods, and provides a simpler, more convenient and efficient method for food quality monitoring and evaluation.
Drawings
FIG. 1 is a chromatogram of the standard obtained in example 1;
FIG. 2 is a standard quality spectrum of acrylamide in example 1;
FIG. 3 is a standard quality spectrum of 2-amino-1-methylimidazo [4,5-b ] quinine (IQ [4,5-b ]) in example 1;
FIG. 4 is a standard quality spectrum of 5-hydroxymethylfurfural in example 1;
FIG. 5 is a standard quality spectrum of 2-amino-1, 6-dimethylimidazo [4,5-b ] pyridine (DMIP) of example 1;
FIG. 6 is a standard quality spectrum of 2-amino-3, 4-dimethylimidazo [4,5-f ] quinoline (MeIQ) of example 1;
FIG. 7 is a standard quality spectrum of 2-amino-3-methylimidazo [4,5-f ] quinoxaline (IQx) of example 1;
FIG. 8 is a standard quality spectrum of 2-amino-1, 5, 6-trimethylimidazo [4,5-b ] pyridine (1, 5, 6-TMIP) of example 1;
FIG. 9 is a standard quality spectrum of 2-amino-3, 8-dimethylimidazo [4,5-f ] quinoxaline (8-MeIQx) of example 1;
FIG. 10 is a standard quality spectrum of 2-amino-3-methylimidazo [4,5-f ] quinoline (IQ) of example 1;
FIG. 11 is a standard quality spectrum of 2-amino-3, 7, 8-trimethylimidazo [4,5-f ] quinoxaline (7, 8-DiMeIQx) of example 1;
FIG. 12 is a standard quality spectrum of 9H-pyrido [3,4-b ] indole (Norharman) of example 1;
FIG. 13 is a standard quality spectrum of 1-methyl-9H-pyrido [3,4-b ] indole (Harman) of example 1;
FIG. 14 is a standard quality spectrum of 2-amino-5-phenylpyridine (Phe-p-1) of example 1;
FIG. 15 is a standard quality spectrum of 2-amino-1-methyl-6-phenylimidazo [4,5-b ] pyridine (PhIP) of example 1;
FIG. 16 is a standard quality spectrum of 2-amino-9H-pyrido [2,3-b ] indole (AαC) of example 1;
FIG. 17 is a standard quality spectrum of 2-amino-3-methyl-9H-pyrido [2,3-b ] indole (MeA. Alpha.C) of example 1;
wherein a is acrylamide, b is 2-amino-1-methylimidazo [4,5-b ] quinine (IQ [4,5-b ]), C is 5-hydroxymethylfurfural, d is 2-amino-1, 6-dimethylimidazo [4,5-b ] pyridine (DMIP), e is 2-amino-3, 4-dimethylimidazo [4,5-f ] quinoline (MeIQ), f is 2-amino-3-methylimidazo [4,5-f ] quinoxaline (IQx), g is 2-amino-1, 5, 6-trimethylimidazo [4,5-b ] pyridine (1, 5, 6-TMIP), H is 2-amino-3, 8-dimethylimidazo [4,5-f ] quinoxaline (8-MeIQx), i is 2-amino-3, 5-f ] quinoline (IQ), j is 2-amino-3, 7, 8-trimethylimidazo [4,5-f ] quinoxaline (IQx), g is 2-amino-1, 5, 6-trimethylimidazo [4,5-b ] pyridine (1, 5, 6-TMIP), H is 2-amino-3, 8-dimethylimidazo [4,5-f ] quinoxaline (8-MeIQx), i is 2-amino-3, 8-dimethylimidazo [4,5-f ] quinoline (IQ) is 2-amino-3, 8-MeIQx), i is 2-amino-3, 6-dimethylimidazo [4,5-b ] quinoxaline (3, 3-MeI) is 2-1, 6-p-dimethylimidazo [4, 8-1-p ] quinoline (P), p is 2-amino-3-methyl-9H-pyrido [2,3-b ] indole (MeAαC).
Detailed Description
S1, preparing an isotope internal standard sample: acrylamide-d is selected 3 And 2-amino-3, 4, 8-trimethylimidazo [4,5-f]Quinoxaline-d 3 (4,8-DiMeIQx-d 3 ) As internal standard, are respectively prepared into final concentration1-2 mug/mL of mixed internal standard working solution;
s2, preparing a standard sample: acrylamide, 5-hydroxymethylfurfural, 2-amino-1, 6-dimethylimidazo [4,5-b ] pyridine (DMIP), 2-amino-1, 5, 6-trimethylimidazo [4,5-b ] pyridine (1, 5, 6-TMIP), 2-amino-1-methyl-6-phenylimidazo [4,5-b ] pyridine (PhIP), 2-amino-3-methylimidazo [4,5-f ] quinoline (IQ), 2-amino-1-methylimidazo [4,5-b ] quinine (IQ [4,5-b ]), 2-amino-3, 4-dimethylimidazo [4,5-f ] quinoline (MeIQ), 2-amino-3-methylimidazo [4,5-f ] quinoxaline (IQx), 2-amino-3, 8-dimethylimidazo [4,5-f ] quinoxaline (8-MeIQx), 2-amino-3, 7, 8-trimethylimidazo [4,5-f ] quinoline (IQ), 2-amino-3, 5-f ] quinoxaline (MeIQx), 2-amino-3, 5-f ] quinoline (MeIQ) and 2-amino-3-methylimidazo [4,5-f ] quinoxaline (MeIQ), 9H-pyrido [3,4-b ] indole (Norharman) and 1-methyl-9H-pyrido [3,4-b ] indole (Harman) are used as standard substances to respectively prepare working solutions with concentrations of 0.10,1.00,10.00,20.00,50.00,100.00,200.00 and 500.00ng/mL, wherein the final concentration of an internal standard in each concentration standard substance is 10-200ng/mL, and the number of standard samples is 5; eluting and separating each object to be detected in the mobile phase through a chromatographic column, and obtaining corresponding retention time through an ultra-high performance liquid chromatography high resolution mass spectrometer;
s3, preparing a detection sample: taking a sample to be detected according to the proportion of 15-20:1 (m/v), adding the sample to be detected into the mixed internal standard working solution prepared by S1, and then, according to the proportion of 1:100 (v/v) homogenizing in a 50% volume fraction acetonitrile in water for 20-30s at 1000-15000rpm using a disperser to obtain a food matrix dispersion;
taking the food matrix dispersion liquid, adding n-hexane solution and anhydrous MgSO according to the ratio of 10:8:1 (v/m/m) 4 Mixing with NaCl, vortex oscillating for 1-3min, centrifuging for 8-10min at 1000-4000g, and taking out all middle layer liquid after obvious layering to obtain sample to be volatilized, namely acetonitrile solution;
drying the sample to be volatilized with nitrogen at room temperature until all liquid is generated, redissolving the sample with 1mL of acetonitrile water solution with volume fraction of 50%, centrifuging at a high speed of 10000-20000g for 8-10min, and taking supernatant after obvious layering to obtain a harmful substance detection sample to be detected;
s4, sample measurement: a Waters HSS T3 (2.1 mm multiplied by 100mm,1.8 mu m) hydrophilic chromatographic column is adopted, and the standard substance prepared in the step S2 and the harmful substance detection sample to be detected prepared in the step S3 are respectively measured through an ultra-high performance liquid chromatography (Thermo Scientific, vanquish) and a mixed quadrupole-orbit mass spectrum (Q exact HF-X) combined instrument to obtain the internal standard of the standard sample and the harmful substance detection sample to be detected and the peak areas of the harmful substance detection sample components to be detected;
the specific detection conditions are as follows:
sample injection amount: 1 μl; acquisition mode: full ms+prm;
mobile phase: phase a is 0.1% formic acid-water solution by volume fraction; phase B is formic acid-acetonitrile solution with volume fraction of 0.1%;
elution flow rate: 0.3mL/min;
elution gradient: 1% B,0min;1% B,0-1.5min;99% B,1.5-16.5min;1% B,16.6-20.0min;
s5, performing linear regression according to the retention time of the standard sample measured in the step S2 and the ratio of the concentration of the standard sample to the areas of the components to be measured and the internal standard peak, so as to obtain a standard curve of the harmful substance;
and (3) taking the ratio of the components to be detected of the harmful substances to be detected obtained in the step (S3) to the internal standard peak area into a standard curve for calculation, and thus obtaining the content of the harmful substances to be detected in the thermally processed food.
Example 1
1. Making a standard curve
Standard sample preparation: acrylamide, 5-hydroxymethyl furfural and 2-amino-1, 6-dimethyl imidazo [4,5-b ] are selected]Pyridine (DMIP), 2-amino-1, 5, 6-trimethylimidazo [4,5-b]Pyridine (1, 5, 6-TMIP), 2-amino-1-methyl-6-phenylimidazo [4,5-b]Pyridine (PhIP), 2-amino-3-methylimidazo [4,5-f]Quinoline (IQ), 2-amino-1-methylimidazo [4,5-b ]]Quinine (IQ [4, 5-b)]) 2-amino-3, 4-dimethylimidazo [4,5-f]Quinoline (MeIQ), 2-amino-3-methylimidazo [4,5-f]Quinoxaline (IQx), 2-amino-3, 8-dimethylimidazo [4,5-f]Quinoxaline (8-MeIQx), 2-amino-3, 7, 8-trimethylimidazo [4,5-f]Quinoxaline (7, 8-DiMeIQx), 2-amino-5-phenylpyridine (Phe-p-1)) 2-amino-9H-pyrido [2,3-b ]]Indole (AαC), 2-amino-3-methyl-9H-pyrido [2,3-b]Indole (MeAαC), 9H-pyrido [3,4-b]Indole (Norharman) and 1-methyl-9H-pyrido [3,4-b]Indole (Harman) is used as a standard substance to prepare working solutions with concentrations of 0.10,1.00,10.00,20.00,50.00,100.00,200.00 and 500.00ng/mL respectively, wherein acrylamide-d is contained in each concentration standard substance 3 And 2-amino-3, 4, 8-trimethylimidazo [4,5-f]Quinoxaline-d 3 (4,8-DiMeIQx-d 3 ) The final concentration of the internal standard was 100ng/mL and the number of standard samples was 5.
Ultra-high performance liquid chromatography (Thermo Scientific, vanquish) combined with mixed quadrupole-orbital mass spectrometry (Q exact HF-X) measurement conditions: sample injection amount: 1 μl; acquisition mode: full ms+prm; mobile phase: phase a is 0.1% formic acid-water solution; phase B is 0.1% formic acid-acetonitrile solution; elution flow rate: 0.3mL/min; elution gradient: 1% B,0min;1% B,0-1.5min;99% B,1.5-16.5min;1% B,16.6-20.0min. The obtained standard substance has chromatogram shown in FIG. 1, mass spectrum shown in FIGS. 2-17, and standard curve equation shown in Table 1, each substance has chromatographic peak with good corresponding peak shape in retention time shown in FIG. 1, linear range is analyzed by linear regression using calibration curve, correlation coefficient (R 2 ) And not less than 0.991.
TABLE 1 retention time and standard curve equation
2. Detecting a sample to be tested
Sample preparation: weighing a sample to be measured of roasted eel, adding 200 mu L of acrylamide-d 3 And 2-amino-3, 4, 8-trimethylimidazo [4,5-f]Quinoxaline-d 3 (4,8-DiMeIQx-d 3 ) The mixture was homogenized in a 20mL volume fraction of 50% acetonitrile in water with a final concentration of 2. Mu.g/mL and 1. Mu.g/mL of the mixed internal standard working solution, respectively5mL of n-hexane solution and 4g of anhydrous MgSO were added 4 And 0.5g of NaCl, vortex shaking for 2min, centrifuging for 10min by using 2000g, obtaining 10mL of acetonitrile solution obtained after centrifugation, drying the acetonitrile solution at normal temperature by using nitrogen until the liquid is completely volatilized, adding 1mL of 50% acetonitrile aqueous solution with volume fraction for redissolving, and centrifuging for 10min at a high speed of 20000 g.
Ultra-high performance liquid chromatography (Thermo Scientific, vanquish) combined with mixed quadrupole-orbital mass spectrometry (Q exact HF-X) measurement conditions: sample injection amount: 1 μl; acquisition mode: full ms+prm; mobile phase: phase a is 0.1% formic acid-water solution; phase B is 0.1% formic acid-acetonitrile solution; elution flow rate: 0.3mL/min; elution gradient: 1% B,0min;1% B,0-1.5min;99% B,1.5-16.5min;1% B,16.6-20.0min.
And carrying out calculation according to the ratio of the components to be detected of the harmful substances to be detected and the internal standard peak area, and carrying out calculation to obtain the contents of three types of harmful substances to be detected in the roasted eel, wherein the contents are represented by the following formula:
standard curve of object to be measured: y=ax+b
Y=peak area of component to be measured/peak area of internal standard
X=content of harmful substance to be measured
The content of each harmful substance is respectively acrylamide: 191.14 + -9.88 μg/kg; 2-amino-1-methyl-6-phenylimidazo [4,5-b ] pyridine (PhIP): 26.66+ -1.73 μg/kg; 2-amino-1, 5, 6-trimethylimidazo [4,5-b ] pyridine (1, 5, 6-TMIP): 106.10 + -4.83 μg/kg; 2-amino-1, 6-dimethylimidazo [4,5-b ] pyridine (DMIP): 15.06+ -1.97 μg/kg; 2-amino-3, 8-dimethylimidazo [4,5-f ] quinoxaline (8-MeIQx): 16.65+ -0.72 μg/kg; 2-amino-5-phenylpyridine (Phe-p-1): 0.11+/-0.03 mug/kg; 9H-pyrido [3,4-b ] indole (Norharman): 66.63 + -1.46 μg/kg; 1-methyl-9H-pyrido [3,4-b ] indole (Harman): 16.25+ -1.07 μg/kg; 2-amino-9H-pyrido [2,3-b ] indole (aαc): 5.28+ -0.72 μg/kg, and no other harmful substances were detected.
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should be covered by the protection scope of the present invention by making equivalents and modifications to the technical solution and the inventive concept thereof.
Claims (7)
1. A method for simultaneously determining harmful substances in food thermal processing, which is characterized by comprising the following steps:
s1, preparing an isotope internal standard sample: acrylamide-d 3 and 2-amino-3, 4, 8-trimethyl imidazo [4,5-f ] quinoxaline-d 3 (4, 8-DiMeIQx-d 3) are selected as internal standards, and are respectively prepared into mixed internal standard working solution with the final concentration of 1-2 mug/mL;
s2, preparing a standard sample: acrylamide, 5-hydroxymethylfurfural, 2-amino-1, 6-dimethylimidazo [4,5-b ] pyridine (DMIP), 2-amino-1, 5, 6-trimethylimidazo [4,5-b ] pyridine (1, 5, 6-TMIP), 2-amino-1-methyl-6-phenylimidazo [4,5-b ] pyridine (PhIP), 2-amino-3-methylimidazo [4,5-f ] quinoline (IQ), 2-amino-1-methylimidazo [4,5-b ] quinine (IQ [4,5-b ]), 2-amino-3, 4-dimethylimidazo [4,5-f ] quinoline (MeIQ), 2-amino-3-methylimidazo [4,5-f ] quinoxaline (IQx), 2-amino-3, 8-dimethylimidazo [4,5-f ] quinoxaline (8-MeIQx), 2-amino-3, 7, 8-trimethylimidazo [4,5-f ] quinoline (IQ), 2-amino-3, 5-f ] quinoxaline (MeIQx), 2-amino-3, 5-f ] quinoline (MeIQ) and 2-amino-3-methylimidazo [4,5-f ] quinoxaline (MeIQ), 9H-pyrido [3,4-b ] indole (Norharman) and 1-methyl-9H-pyrido [3,4-b ] indole (Harman) are used as standard substances to respectively prepare working solutions with concentrations of 0.10,1.00,10.00,20.00,50.00,100.00,200.00 and 500.00ng/mL, wherein the final concentration of an internal standard in each concentration standard substance is 10-200ng/mL, and the number of standard samples is 5; eluting and separating each object to be detected in the mobile phase through a chromatographic column, and obtaining corresponding retention time through an ultra-high performance liquid chromatography high resolution mass spectrometer;
s3, preparing a detection sample: taking a sample to be detected according to the proportion of 15-20:1 (m/v), adding the sample to be detected into the mixed internal standard working solution prepared by S1, and homogenizing for 20-30S in an acetonitrile water solution with the volume fraction of 50% according to the proportion of 1:100 (v/v) by using a disperser at the rotating speed of 1000-15000rpm to prepare a food matrix dispersion;
taking the food matrix dispersion according to 10:8:1 (v +.m/m) adding n-hexane solution, anhydrous MgSO 4 Mixing with NaCl, vortex oscillating for 1-3min, centrifuging for 8-10min at 1000-4000g, and taking out all middle layer liquid after obvious layering to obtain sample to be volatilized, namely acetonitrile solution;
drying the sample to be volatilized with nitrogen at room temperature until all liquid is generated, redissolving the sample with 1mL of acetonitrile water solution with volume fraction of 50%, centrifuging at a high speed of 10000-20000g for 8-10min, and taking supernatant after obvious layering to obtain a harmful substance detection sample to be detected;
s4, sample measurement: a Waters HSS T3 (2.1 mm multiplied by 100mm,1.8 mu m) hydrophilic chromatographic column is adopted, and the standard substance prepared in the step S2 and the harmful substance detection sample to be detected prepared in the step S3 are respectively measured through an ultra-high performance liquid chromatography (Thermo Scientific, vanquish) and a mixed quadrupole-orbit mass spectrum (Qexact HF-X) combined instrument to obtain the internal standard of the standard sample and the harmful substance detection sample to be detected and the peak areas of the harmful substance detection sample components to be detected;
the specific detection conditions are as follows:
sample injection amount: 1 μl; acquisition mode: full ms+prm;
mobile phase: phase a is 0.1% formic acid-water solution by volume fraction; phase B is formic acid-acetonitrile solution with volume fraction of 0.1%;
elution flow rate: 0.3mL/min;
elution gradient: 1% B,0min;1% B,0-1.5min;99% B,1.5-16.5min;1% B,16.6-20.0min;
s5, performing linear regression according to the retention time of the standard sample measured in the step S2 and the ratio of the concentration of the standard sample to the areas of the components to be measured and the internal standard peak, so as to obtain a standard curve of the harmful substance;
and (3) taking the ratio of the components to be detected of the harmful substances to be detected obtained in the step (S3) to the internal standard peak area into a standard curve for calculation, and thus obtaining the content of the harmful substances to be detected in the thermally processed food.
2. The method according to claim 1, wherein the determination in step S4 is performed by ultra-high performance liquid chromatography and mixed quadrupole-rail mass spectrometry using a Waters HSS T3 (2.1 mm x 100mm,1.8 μm) hydrophilic chromatography column.
3. The method for simultaneously determining harmful substances in the thermal processing of food according to claim 2, wherein the specific detection conditions are as follows:
sample injection amount: 1 μl; acquisition mode: full ms+prm;
mobile phase: phase a is 0.1% formic acid-water solution by volume fraction; phase B is formic acid-acetonitrile solution with volume fraction of 0.1%;
elution flow rate: 0.3mL/min;
elution gradient: 1% B,0min;1% B,0-1.5min;99% B,1.5-16.5min;1% B,16.6-20.0min.
4. The method for simultaneously determining harmful substances in food thermal processing according to claim 1, wherein the preparation method of the mixed internal standard working solution in step S1 is as follows: acrylamide-d 3 and 2-amino-3, 4, 8-trimethyl imidazo [4,5-f ] quinoxaline-d 3 (4, 8-DiMeIQx-d 3) are used as internal standards to prepare mixed internal standard working solutions with the final concentration of 1-2 mug/mL respectively.
5. The method for simultaneous determination of harmful substances in food heat processing according to claim 1, wherein the drying method in step S3 is: nitrogen drying at room temperature until the liquid had evaporated.
6. The method for simultaneous determination of harmful substances in food heat processing according to claim 1, wherein the standard sample preparation method in step S4 is as follows: acrylamide, 5-hydroxymethylfurfural, 2-amino-1, 6-dimethylimidazo [4,5-b ] pyridine (DMIP), 2-amino-1, 5, 6-trimethylimidazo [4,5-b ] pyridine (1, 5, 6-TMIP), 2-amino-1-methyl-6-phenylimidazo [4,5-b ] pyridine (PhIP), 2-amino-3-methylimidazo [4,5-f ] quinoline (IQ), 2-amino-1-methylimidazo [4,5-b ] quinine (IQ [4,5-b ]), 2-amino-3, 4-dimethylimidazo [4,5-f ] quinoline (MeIQ), 2-amino-3-methylimidazo [4,5-f ] quinoxaline (IQx), 2-amino-3, 8-dimethylimidazo [4,5-f ] quinoxaline (8-MeIQx), 2-amino-3, 7, 8-trimethylimidazo [4,5-f ] quinoline (IQ), 2-amino-3, 5-f ] quinoxaline (MeIQx), 2-amino-3, 5-f ] quinoline (MeIQ) and 2-amino-3-methylimidazo [4,5-f ] quinoxaline (MeIQ), 9H-pyrido [3,4-b ] indole (Norharman) and 1-methyl-9H-pyrido [3,4-b ] indole (Harman) are used as standard substances to prepare working solutions with concentrations of 0.10,1.00,10.00,20.00,50.00,100.00,200.00 and 500.00ng/mL respectively, wherein the final concentration of an internal standard in each concentration standard substance is 100-200ng/mL.
7. The method for simultaneously determining harmful substances in heat processing of food according to claim 1, wherein the calculating method of the content of harmful substances to be detected in step S5 is as follows:
standard curve of object to be measured: y=ax+b
Y=peak area of component to be measured/peak area of internal standard
X=the content of the pest to be measured.
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