CN104297399A - Method for detecting byproducts 4-methylimidazole and 2-acetyl-4-hydroxy-butylimidazole in caramel pigment - Google Patents
Method for detecting byproducts 4-methylimidazole and 2-acetyl-4-hydroxy-butylimidazole in caramel pigment Download PDFInfo
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Abstract
A method for detecting byproducts 4-methylimidazole and 2-acetyl-4-hydroxy-butylimidazole in a caramel pigment comprises the following steps: 1, preparing a solution of a sample to be detected; 2, detecting the sample; and 3, analyzing result. The method has the advantages of rapid detection, high sensitivity, high accuracy and the like.
Description
Technical field
The present invention relates to the detection method of accessory substance 4-methylimidazole and 2-acetyl group-4-hydroxy-butyl imidazoles in a kind of burnt sugar coloring, belong to the method for inspection of food safety detection.
Background technology
4-methylimidazole (4-Methylimidazole, 4-MEI) be a kind of accessory substance that Maillard reaction in III and IV class burnt sugar coloring process of manufacture (Maillard browning model systems) produces, have research display, it can induced tumor.EFSA (EFSA) reports; III class burnt sugar coloring also can produce 2-acetyl group-4-hydroxy-butyl imidazoles (2-acetyl-4-tetrahydroxy-butylimidazole in process of manufacture; THI), this material has immunotoxicity.
At present, to the mensuration of 4-MEI content in caramel colorant, China has food additives burnt sugar coloring standard GB/T 8817-2001 only, and in caramel colorant, the mensuration of THI does not have national standard.In the world, in the World Food Programme/WTO food additives joint specialist council (JECFA) burnt sugar coloring specification of quality JECFA-2011,4-MEI and THI adopts the derivatization method of gas chromatography and liquid chromatography to detect respectively respectively.According to literature search, in existing caramel colorant, the assay method of accessory substance 4-MEI and THI is nearly following several: thin-layered chromatography, vapor-phase chromatography, liquid phase chromatography, the chromatography of ions, capillary electrophoresis, compounds GC-MS technology, liquid-mass chromatography technology.Wherein, several technology mostly needs more complicated pretreatment technology, and this is very disadvantageous for a large amount of sample analysis.Liquid phase chromatography UV-detector can detect two kinds of materials simultaneously, and due to the restriction of sensitivity, the sampling amount that so complicated sample substrate is relatively large is very high to the requirement of pretreatment technology.Therefore, current can the detection method of accessory substance 4-MEI and THI in rapid and accurate determination burnt sugar coloring in the urgent need to setting up.
Summary of the invention
1. the object of the present invention is to provide a kind of method that in burnt sugar coloring, accessory substance 4-MEI and THI detects simultaneously, the preparation of the method comprises the steps: (1) testing sample solution; (2) sample detection; (3) interpretation of result.
(1) preparation of testing sample solution comprises following concrete steps:
A () prepares Solid-Phase Extraction load solution: take caramel colorant sample 1g (accurately to 0.001g), be placed in 100mL volumetric flask, add water and be settled to scale.Get the above-mentioned sample solution of 0.1mL, add 0.1mL hydrochloric acid solution (0.02moL/L), add 0.2mL inner mark solution D6-4-methylimidazole (D6-4-Methylimidazole, D6-4-MEI, 1.0 μ g/mL), add water and be settled to 2mL, after mixing, treat homophase extracting and purifying.
B () solid-phase extraction column activates: select mixed type cation exchange solid-phase extraction column, matrix is polystyrene-divinylbenzene superpolymer, 60mg, 3mL, successively with 2mL methyl alcohol, the activation of 2mL water before using.
(c) Solid-Phase Extraction: the sample solution (a) prepared adds in the pillar just activated in (b), coutroi velocity is less than 0.5mL/min, drain, add 1mL water and the drip washing of 1mL methyl alcohol, coutroi velocity is less than 1.0mL/min, drains, and collects with eluent (ammoniacal liquor+methyl alcohol=5+95 (v/v)) 2mL wash-out, coutroi velocity is less than 0.5mL/min, drains.To collect liquid lower than under 50 DEG C of conditions, nitrogen dries up, residue 0.5mL solution (ammoniacal liquor+acetonitrile+water=0.05+5+94.95 (v/v)) constant volume, vortex mixed 1min, cross 0.22 μm of water system miillpore filter, i.e. obtained testing sample solution, inner mark method ration.
In embodiment of the present invention, weigh 1g sample constant volume in step (a) in 100mL water, get 0.1 ~ 0.2mL sample solution and prepare Solid-Phase Extraction, preferred 0.1mL, load solution adds water and is settled to 2 ~ 3mL, preferred 2mL.
In embodiment of the present invention, 1 ~ 2mL water and the drip washing of 1 ~ 2mL methyl alcohol in step (c), preferred 1mL water and the drip washing of 1mL methyl alcohol, preferred 2mL elution.Collect liquid to dry up under lower than 50 DEG C of conditions or spin concentration volatilizes, residue needs vortex 1min or ultrasound wave within 30 seconds, dissolve and cross 0.22 μm of water system miillpore filter after adding constant volume solution.
(2) sample detection comprises following concrete steps:
A the preparation of () standard solution: accurately take 4-MEI, THI and D6-4-MEI standard items respectively, uses water-soluble solution, be made into the stock solution of 0.5mg/mL respectively, and during use, the standard that is diluted with water to uses solution.
B (), with liquid chromatography-mass spectrography/mass spectrum (LC-MS/MS) instrument, is furnished with electric spray ion source (ESI) and measures testing sample solution and standard solution.Instrument reference conditions are as follows:
Liquid phase chromatogram condition
Chromatographic column: Polaris C18-A post (2.1mm × 150mm, 3 μm).
Mobile phase: A is 0.05% ammonia spirit; B is acetonitrile.Condition of gradient elution is in table 1
Column temperature: 30 DEG C
Sample size: 10 μ L
Flow velocity: 0.4mL/min
Table 1 liquid phase condition of gradient elution
Mass detector condition:
Ionization mode: H-ESI ionizes, positive ion
Ion spray voltage: positive ion 4000v
Volatile Gas temperature: 400 DEG C
Capillary temperature: 270 DEG C
Sheath gas: 60Arb
Assisted gas: 15Arb
Collision gas: argon gas
Scan pattern: multiple-reaction monitoring (MRM), each ion parameters refers to table 2
Table 2 multiple-reaction monitoring (MRM)
Measure the quantitative daughter ion peak area of each compound, D6-4-MEI is interior mark, then make 4-MEI (THI) and interior target peak area ratio-4-MEI (THI) concentration (ng/mL) typical curve respectively, curvilinear equation is shown in formula (1):
y＝ax+b ………(1)
In formula: x---the ratio of 4-MEI or THI peak area and internal standard compound matter D6-4-MEI peak area;
The concentration of y---4-MEI or THI, unit is sodium gram every milliliter (ng/mL).
(3) interpretation of result comprises following concrete steps:
The mensuration of (a) sample solution: in sample to be tested solution, the response of 4-MEI or THI should in the typical curve range of linearity, exceed the range of linearity then should dilute after sample introduction analysis again.
B () qualitatively judges: measure sample and standard working solution, if the mass chromatography peak retention time consistent with standard working solution (variation range is within ± 2.5%) in sample according to above-mentioned condition; In sample, the relative abundance of the relative abundance of two daughter ions of target compound standard solution suitable for concentration is consistent, and relative abundance deviation is no more than the regulation of table 3, then can there is target compound 4-MEI or THI in judgement sample.
The maximum allowable offset of the qualitative ion relative abundance of table 3
The statement of (c) analysis result:
In sample, 4-MEI (THI) content presses formula (2) calculating:
In formula:
X---the content of 4-MEI or THI in sample, unit is grams per kilogram (mg/kg);
C---checked in the concentration of 4-MEI or THI in sample sample introduction liquid by typical curve, unit is sodium gram every milliliter (ng/mL);
C
0---checked in the concentration of 4-MEI or THI in blank sample sample introduction liquid by typical curve, unit is sodium gram every milliliter (ng/mL);
Liquid cumulative volume prepared by V---sample, and unit is milliliter (mL);
M---sample mass, unit is gram (g);
Result retains three position effective digitals.
The feasibility of detection method confirms:
Compound concentration is respectively 4-MEI and the THI standard working solution of 0.010 μ g/mL, 0.020 μ g/mL, 0.050 μ g/mL, 0.10 μ g/mL, 0.20 μ g/mL, 0.50 μ g/mL and 1.0 μ g/mL, optimize pre-treating method be separated testing conditions under carry out range of linearity test, 4-MEI and THI linearly dependent coefficient can reach more than 0.9994 and 0.999.
The detection limit of method and quantitative limit are the indexs of balancing method sensitivity.This method detection limit with the concentration corresponding to the ratio of 3 times of signals and noise for theoretical detection limit, with the concentration corresponding to the ratio of 10 times of signals and noise for theoretical quantitative limit.According to the theoretical detection limit concentration calculated and theoretical quantitative limit concentration, be mixed with machine on a series of standard working solution, determine actual detection limit concentration and actual quantification limit concentration with actual conditions.
The theoretical detection limit of the method 4-MEI and THI and theoretical quantitative limit concentration are respectively 0.001 μ g/mL, 0.003 μ g/mL.Be mixed with machine on actual standard working solution, determine that acceptable detection limit and quantitative limit concentration are respectively 0.003 μ g/mL, 0.010 μ g/mL according to actual conditions.So when being sampled as 1mg, after pre-treatment, final constant volume is to 1.0mL, and detecting of obtaining is limited to 3mg/kg, is quantitatively limited to 10mg/kg.
Sample recovery of standard addition measures:
Adopt the detection method of accessory substance 4-MEI and THI in burnt sugar coloring of the present invention, three concentration levels are added (see table 4 in burnt sugar coloring, 10mg/kg, 20mg/kg, 200mg/kg) mixed standard solution of 4-MEI and THI carries out recovery of standard addition experiment, experimental procedure is with sample detection step, each concentration repeats 6 times, the results are shown in Table the recovery of standard addition of 4,4-MEI and THI respectively between 88.3 ~ 103.5% and 85.3 ~ 101.7%.
The accuracy experiment of table 4 method
The method that the present invention detects accessory substance 4-MEI and THI in burnt sugar coloring can effective isolation of purified for burnt sugar coloring, and measurement result accurately and reliably.
Accompanying drawing explanation
Fig. 1 is the LC-MS/MS multiple-reaction monitoring mass chromatogram adding THI and 4-MEI standard solution
Fig. 2 is the LC-MS/MS multiple-reaction monitoring mass chromatogram of burnt sugar coloring sample
In the accompanying drawings, horizontal ordinate is retention time (minute), and ordinate is relative abundance.
1.4-methylimidazole (4-Methylimidazole, 4-MEI); 2.D6-4-methylimidazole (D6-4-Methylimidazole, D6-4-MEI); 3.2-acetyl group-4-hydroxy-butyl imidazoles (2-acetyl-4-tetrahydroxy-butylimidazole, THI)
Embodiment
Embodiment
(1) preparation of testing sample solution comprises following concrete steps:
A () prepares Solid-Phase Extraction load solution: take caramel colorant sample 1g (accurately to 0.001g), be placed in 100mL volumetric flask, add water and be settled to scale.Get the above-mentioned sample solution of 0.1mL, add 0.1mL hydrochloric acid solution (0.02moL/L), add 0.2mL inner mark solution (D6-4-MEI, 1.0 μ g/mL), add water and be settled to 2mL, after mixing, treat Solid phase extraction.
B () solid-phase extraction column activates: select mixed type cation exchange solid-phase extraction column, matrix is polystyrene-divinylbenzene superpolymer, 60mg, 3mL, or suitable person.Successively with 2mL methyl alcohol, the activation of 2mL water before using.
(c) Solid-Phase Extraction: the sample solution (a) prepared adds in the pillar just activated in (b), coutroi velocity is less than 0.5mL/min, drain, add 1mL water and the drip washing of 1mL methyl alcohol, coutroi velocity is less than 1.0mL/min, drains, and collects with eluent (ammoniacal liquor+methyl alcohol=5+95 (v/v)) 2mL wash-out, coutroi velocity is less than 0.5mL/min, drains.To collect liquid lower than under 50 DEG C of conditions, nitrogen dries up, residue 0.5mL solution (ammoniacal liquor+acetonitrile+water=0.05+5+94.5 (v/v)) constant volume, vortex mixed 1min, cross 0.22 μm of water system miillpore filter, i.e. obtained testing sample solution, inner mark method ration.
(2) sample detection comprises following concrete steps:
A the preparation of () standard solution: accurately take 4-MEI, THI and D6-4-MEI standard items respectively, uses water-soluble solution, be made into the stock solution of 0.5mg/mL respectively, and during use, the standard that is diluted with water to uses solution.
B (), with liquid chromatography-mass spectrography/mass spectrum (LC-MS/MS) instrument, is furnished with electric spray ion source (ESI) and measures testing sample solution and standard solution.Instrument reference conditions are as follows:
Liquid phase chromatogram condition
Chromatographic column: Polaris C18-A post (2.1mm × 150mm, 3 μm).
Mobile phase: A is 0.05% ammonia spirit; B is acetonitrile.Condition of gradient elution is in table 1
Column temperature: 30 DEG C
Sample size: 10 μ L
Flow velocity: 0.4mL/min
Mass detector condition:
Ionization mode: H-ESI ionizes, positive ion
Ion spray voltage: positive ion 4000v
Volatile Gas temperature: 400 DEG C
Capillary temperature: 270 DEG C
Sheath gas: 60Arb
Assisted gas: 15Arb
Collision gas: argon gas
Scan pattern: multiple-reaction monitoring (MRM), each ion parameters refers to table 2
Measure the quantitative daughter ion peak area of each compound, D6-4-MEI is interior mark, then make 4-MEI (THI) and interior target peak area ratio-4-MEI (THI) concentration (ng/mL) typical curve respectively, curvilinear equation is shown in formula (1):
y＝ax+b ………(1)
In formula: x---the ratio of 4-MEI or THI peak area and internal standard compound matter D6-4-MEI peak area;
The concentration of y---4-MEI or THI, unit is sodium gram every milliliter (ng/mL).
Detect any burnt sugar coloring sample with said method, testing result is as following table 5:
Table 5 sample detection result
Claims (5)
1. the detection method of accessory substance 4-methylimidazole and 2-acetyl group-4-hydroxy-butyl imidazoles in burnt sugar coloring, the preparation of the method comprises the steps: (1) testing sample solution; (2) sample detection; (3) interpretation of result.It is characterized in that, wherein the preparation of step (1) testing sample solution comprises following concrete steps:
A () prepares Solid-Phase Extraction load solution: take caramel colorant sample 1g (accurately to 0.001g), be placed in 100mL volumetric flask, add water and be settled to scale.Get the above-mentioned sample solution of 0.1mL, add 0.1mL hydrochloric acid solution (0.02moL/L), add 0.2mL inner mark solution (D6-4-MEI, 1.0 μ g/mL), add water and be settled to 2mL, after mixing, treat Solid phase extraction.
B () solid-phase extraction column activates: select mixed type cation exchange solid-phase extraction column, matrix is polystyrene-divinylbenzene superpolymer, 60mg, 3mL.Successively with 2mL methyl alcohol, the activation of 2mL water before using.
(c) Solid-Phase Extraction: the sample solution (a) prepared adds in the pillar just activated in (b), coutroi velocity is less than 0.5mL/min, drain, add 1mL water and the drip washing of 1mL methyl alcohol, coutroi velocity is less than 1.0mL/min, drains, and collects with eluent (ammoniacal liquor+methyl alcohol=5+95 (v/v)) 2mL wash-out, coutroi velocity is less than 0.5mL/min, drains.To collect liquid lower than under 50 DEG C of conditions, nitrogen dries up, residue 0.5mL solution (ammoniacal liquor+acetonitrile+water=0.05+5+94.5 (v/v)) constant volume, vortex mixed 1min, cross 0.22 μm of water system miillpore filter, i.e. obtained testing sample solution, inner mark method ration.
Step (2) sample detection comprises following concrete steps:
The preparation of (a) standard solution: accurately take 4-methylimidazole (4-Methylimidazole respectively; 4-MEI), 2-acetyl group-4-hydroxy-butyl imidazoles (2-acetyl-4-tetrahydroxy-butylimidazole; and D6-4-methylimidazole (D6-4-Methylimidazole THI); D6-4-MEI) standard items; use water-soluble solution; be made into the stock solution of 0.5mg/mL respectively, during use, the standard that is diluted with water to uses solution.
B (), with liquid chromatography-mass spectrography/mass spectrum (LC-MS/MS) instrument, is furnished with electric spray ion source (ESI) and measures testing sample solution and standard solution.Instrument reference conditions are as follows:
Liquid phase chromatogram condition
Chromatographic column: Polaris C18-A post (2.1mm × 150mm, 3 μm).
Mobile phase: A is 0.05% ammonia spirit; B is acetonitrile.Condition of gradient elution is in table 1
Column temperature: 30 DEG C
Sample size: 10 μ L
Flow velocity: 0.4mL/min
Table 1 liquid phase condition of gradient elution
Mass detector condition:
Ionization mode: H-ESI ionizes, positive ion
Ion spray voltage: positive ion 4000v
Volatile Gas temperature: 400 DEG C
Capillary temperature: 270 DEG C
Sheath gas: 60Arb
Assisted gas: 15Arb
Collision gas: argon gas
Scan pattern: multiple-reaction monitoring (MRM), each ion parameters refers to table 2
Table 2 multiple-reaction monitoring (MRM)
Measure quantitative daughter ion peak area, D6-4-MEI is interior mark, and then make 4-MEI (THI) and interior target peak area ratio-4-MEI (THI) concentration (ng/mL) typical curve respectively, curvilinear equation is shown in formula (1):
y＝ax+b ………(1)
In formula: x---the ratio of 4-MEI or THI peak area and internal standard compound matter D6-4-MEI peak area;
The concentration of y---4-MEI or THI, unit is sodium gram every milliliter (ng/mL).
Step (3) interpretation of result comprises following concrete steps:
The mensuration of (a) sample solution: in sample to be tested solution, the response of 4-MEI or THI should in the typical curve range of linearity, exceed the range of linearity then should dilute after sample introduction analysis again.
B () qualitatively judges: measure sample and standard working solution, if the mass chromatography peak retention time consistent with standard working solution (variation range is within ± 2.5%) in sample according to above-mentioned condition; In sample, the relative abundance of the relative abundance of two daughter ions of target compound standard solution suitable for concentration is consistent, and relative abundance deviation is no more than the regulation of table 3, then can there is target compound 4-MEI or THI in judgement sample.
The maximum allowable offset of the qualitative ion relative abundance of table 3
The statement of (c) analysis result:
In sample, 4-MEI (THI) content presses formula (2) calculating:
In formula:
X---the content of 4-MEI or THI in sample, unit is grams per kilogram (mg/kg);
C---checked in the concentration of 4-MEI or THI in sample sample introduction liquid by typical curve, unit is sodium gram every milliliter (ng/mL);
C
0---checked in the concentration of 4-MEI or THI in blank sample sample introduction liquid by typical curve, unit is sodium gram every milliliter (ng/mL);
Liquid cumulative volume prepared by V---sample, and unit is milliliter (mL);
M---sample mass, unit is gram (g);
Result retains three position effective digitals.
2. the detection method of accessory substance 4-methylimidazole and 2-acetyl group-4-hydroxy-butyl imidazoles in a kind of burnt sugar coloring in claim 1; it is characterized in that; 1g sample is dissolved in 100mL water; get 0.1mL sample solution; add 0.02moL/L hydrochloric acid solution 0.1mL; add interior mark, add water and be settled to 2mL, after mixing, treat Solid phase extraction.
3. select mixed type cation exchange solid-phase extraction column to purify described in claim 1, successively with 2mL methyl alcohol, the activation of 2mL water before using.
4. in claim 1, in solid phase extraction procedure, sample solution adds in the pillar just activated, characteristic is that controlling loading flow velocity is less than 0.5mL/min, drain, add 1mL water and the drip washing of 1mL methyl alcohol, coutroi velocity is less than 1.0mL/min, drains, and is that ammoniacal liquor+methyl alcohol=5+95 (v/v) 2mL wash-out is collected by eluent ratio, coutroi velocity is less than 0.5mL/min, drains.
5. in claim 1, sample detection process characteristic is to use Polaris C18-A post to detect, and mobile phase: A is 0.05% ammonia spirit; B is acetonitrile.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104833744A (en) * | 2015-06-05 | 2015-08-12 | 上海浩登材料科技有限公司 | Detection method for 4-methylimidazole in food |
| CN109856288A (en) * | 2019-03-29 | 2019-06-07 | 贵州省分析测试研究院 | A kind of method of 4-methylimidazole in detection soy sauce |
| CN110658285A (en) * | 2019-11-18 | 2020-01-07 | 浙江省疾病预防控制中心 | Method for rapidly detecting contents of 2-methylimidazole and 4-methylimidazole in caramel color |
| CN115343393A (en) * | 2022-08-23 | 2022-11-15 | 福建省纤维检验中心 | Method for detecting 1-vinyl imidazole in fabric |
| CN115487667A (en) * | 2022-09-15 | 2022-12-20 | 湖南湘渝科技有限公司 | Tail gas absorption process for caramel color production by using common method |
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| EP0212049A2 (en) * | 1985-08-26 | 1987-03-04 | D.D. Williamson Co., Inc. | Process for production of concentrated salt stable and beer stable ammonia caramel color under superatmospheric pressure conditions |
| CA2797972A1 (en) * | 2004-05-20 | 2005-12-01 | Pioneer Hi-Bred International, Inc. | Maize multidrug resistance-associated protein polynucleotides and methods of use |
| CN102062768A (en) * | 2009-11-13 | 2011-05-18 | 天津市食品研究所有限公司 | Method for quickly detecting 4-methylimidazole in food |
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| EP0212049A2 (en) * | 1985-08-26 | 1987-03-04 | D.D. Williamson Co., Inc. | Process for production of concentrated salt stable and beer stable ammonia caramel color under superatmospheric pressure conditions |
| CA2797972A1 (en) * | 2004-05-20 | 2005-12-01 | Pioneer Hi-Bred International, Inc. | Maize multidrug resistance-associated protein polynucleotides and methods of use |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104833744A (en) * | 2015-06-05 | 2015-08-12 | 上海浩登材料科技有限公司 | Detection method for 4-methylimidazole in food |
| CN109856288A (en) * | 2019-03-29 | 2019-06-07 | 贵州省分析测试研究院 | A kind of method of 4-methylimidazole in detection soy sauce |
| CN110658285A (en) * | 2019-11-18 | 2020-01-07 | 浙江省疾病预防控制中心 | Method for rapidly detecting contents of 2-methylimidazole and 4-methylimidazole in caramel color |
| CN110658285B (en) * | 2019-11-18 | 2022-03-25 | 浙江省疾病预防控制中心 | Method for rapidly detecting contents of 2-methylimidazole and 4-methylimidazole in caramel color |
| CN115343393A (en) * | 2022-08-23 | 2022-11-15 | 福建省纤维检验中心 | Method for detecting 1-vinyl imidazole in fabric |
| CN115343393B (en) * | 2022-08-23 | 2023-09-26 | 福建省纤维检验中心 | Method for detecting 1-vinyl imidazole in fabric |
| CN115487667A (en) * | 2022-09-15 | 2022-12-20 | 湖南湘渝科技有限公司 | Tail gas absorption process for caramel color production by using common method |
| CN115487667B (en) * | 2022-09-15 | 2024-03-26 | 湖南湘渝科技有限公司 | Tail gas absorption process for caramel color production by common method |
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