CN104297399B - By-product 4-methylimidazole and the detection method of 2-acetyl group-4-hydroxy-butyl imidazoles in caramel color - Google Patents
By-product 4-methylimidazole and the detection method of 2-acetyl group-4-hydroxy-butyl imidazoles in caramel color Download PDFInfo
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Abstract
By-product 4 Methylimidazole. and the detection method of 2 acetyl 4 hydroxybutyl imidazoles in a kind of caramel color, the method comprises the steps: the preparation of (1) testing sample solution；(2) sample detection；(3) interpretation of result.The method has quickly detection, high sensitivity, accuracy advantages of higher.
Description
Technical field
The present invention relates to by-product 4-methylimidazole and 2-acetyl group-4-hydroxy-butyl imidazoles in a kind of caramel color
Detection method, belongs to the method for inspection of food safety detection.
Background technology
4-methylimidazole (4-Methylimidazole, 4-MEI) is in III and IV class caramel color process of manufacture
A kind of by-product that Maillard reaction (Maillard browning model systems) produces, has research display, and it can
Induced tumor.EFSA (EFSA) reports, Group III caramel color also can produce 2-second in process of manufacture
Acyl group-4-hydroxy-butyl imidazoles (2-acetyl-4-tetrahydroxy-butylimidazole, THI), this material has exempts from
Epidemic disease toxicity.
At present, to the mensuration of 4-MEI content in caramel color, China has food additive caramel color standard GB/T only
8817-2001, in caramel color, the mensuration of THI does not has national standard.In the world, the World Food Programme/WTO food additive connection
Close 4-MEI and THI in the Committee of Experts (JECFA) caramel color specification of quality JECFA-2011 and be respectively adopted gas chromatogram and liquid
The derivatization method of phase chromatograph detects respectively.According to literature search, the survey of by-product 4-MEI and THI in existing caramel color
Method of determining is about following several: thin layer chromatography, gas chromatography, liquid chromatography, the chromatography of ions, capillary electrophoresis
Method, compounds GC-MS technology, liquid-mass chromatography technology.Before wherein, several technology are required for greatly more complicated pretreatment technology, and this is right
It is the most disadvantageous in substantial amounts of sample analysis.Liquid chromatography UV-detector can detect two kinds of materials simultaneously, due to sensitive
The restriction of degree, the sampling amount that the most complicated sample substrate is relatively large is the highest to the requirement of pretreatment technology.Therefore, currently
Can the detection method of by-product 4-MEI and THI in rapid and accurate determination caramel color in the urgent need to setting up.
Summary of the invention
1. it is an object of the invention to provide a kind of method that in caramel color, by-product 4-MEI and THI detects simultaneously, should
Method comprises the steps:
(1) preparation of testing sample solution；(2) sample detection；(3) interpretation of result.
(1) preparation of testing sample solution comprises the following specific steps that:
A () prepares Solid-Phase Extraction load solution: weigh caramel color sample 1g (accurately to 0.001g), is placed in 100mL and holds
In measuring bottle, add water and be settled to scale.Take 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), adds water and is settled to
2mL, treats Solid phase extraction after mixing.
B () solid-phase extraction column activates: selecting mixed type cation exchange solid-phase extraction column, substrate is polystyrene-diethyl
Alkenyl benzene high polymer, 60mg, 3mL, successively with 2mL methanol, the activation of 2mL water before using.
(c) Solid-Phase Extraction: the sample solution (a) prepared adds in the pillar just activated in (b), and coutroi velocity is little
In 0.5mL/min, draining, add 1mL water and 1mL methanol drip washing, coutroi velocity is less than 1.0mL/min, drains, uses eluent
(ammonia+methanol=5+95 (v/v)) 2mL eluting is collected, and coutroi velocity is less than 0.5mL/min, drains.Liquid will be collected less than 50
Under the conditions of DEG C, nitrogen dries up, residue 0.5mL solution (ammonia+acetonitrile+water=0.05+5+94.95 (v/v)) constant volume, and vortex mixes
Close 1min, cross 0.22 μm water system microporous filter membrane, i.e. prepare testing sample solution, inner mark method ration.
In embodiment of the present invention, in step (a) middle weighing 1g sample constant volume to 100mL water, take 0.1～0.2mL sample
Product solution prepares Solid-Phase Extraction, preferably 0.1mL, and load solution adds water and is settled to 2～3mL, preferably 2mL.
In embodiment of the present invention, 1～2mL water and 1～2mL methanol drip washing, preferably 1mL water and 1mL first in step (c)
Alcohol drip washing, preferably 2mL elution.Collection liquid can dry up under the conditions of less than 50 DEG C or spin concentration volatilizes, residue
Vortex 1min or ultrasound wave is needed within 30 seconds, to dissolve and cross 0.22 μm water system microporous filter membrane after adding constant volume solution.
(2) sample detection comprises the following specific steps that:
A the preparation of () standard solution: the most accurately weigh 4-MEI, THI and D6-4-MEI standard substance, with water dissolution, divides
Not being made into the stock solution of 0.5mg/mL, 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).
Flowing phase: A is 0.05% ammonia spirit；B is acetonitrile.Condition of gradient elution is shown 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, cation
Ion spray voltage: cation 4000v
Volatile Gas temperature: 400 DEG C
Capillary temperature: 270 DEG C
Sheath gas: 60Arb
Auxiliary gas: 15Arb
Collision gas: argon
Scan pattern: multiple-reaction monitoring (MRM), each ion parameters refers to table 2
Table 2 multiple-reaction monitoring (MRM)
Measuring each compound quantitative daughter ion peak area, D6-4-MEI is internal standard, makees 4-MEI (THI) the most respectively with interior
Target peak area ratio 4-MEI (THI) concentration (ng/mL) standard curve, curvilinear equation is shown in formula (1):
Y=ax+b (1)
In formula: x 4-MEI or THI peak area and the ratio of internal standard material D6-4-MEI peak area；
The concentration of y 4-MEI or THI, unit is nanograms per milliliter (ng/mL).
(3) interpretation of result comprises the following specific steps that:
The mensuration of (a) sample solution: in sample to be tested solution, the response value of 4-MEI or THI should be at the linear model of standard curve
In enclosing, exceed sample introduction analysis again after the range of linearity then should dilute.
B () qualitatively judges: measure sample and standard working solution according to above-mentioned condition, if the mass chromatography peak in sample
Retention time consistent with standard working solution (excursion is within ± 2.5%)；In sample two sons of target compound from
The relative abundance of the relative abundance solution fairly standard with concentration of son is consistent, and relative abundance deviation less than the regulation of table 3, then may be used
Judgement sample exists target compound 4-MEI or THI.
The maximum allowable offset of table 3 qualitative ion relative abundance
The statement of (c) analysis result:
In sample 4-MEI (THI) content press formula (2) calculate:
X=(C-C0)×V×103/m/106……………………………………(2)
In formula:
The content of 4-MEI or THI in X sample, unit is milligrams per kilogram (mg/kg)；
C is checked in the concentration of 4-MEI or THI in sample sample introduction liquid by standard curve, and unit is nanograms per milliliter (ng/
mL)；
C0Being checked in the concentration of 4-MEI or THI in blank sample sample introduction liquid by standard curve, unit is nanograms per 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 be respectively 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 4-MEI and the THI standard working solution of 1.0 μ g/mL, under the conditions of the pre-treating method optimized and separation detection
Carrying out range of linearity test, 4-MEI and THI linearly dependent coefficient can reach 0.9994 and more than 0.999.
The detection limit of method and quantitative limit are the indexs of balancing method sensitivity.This method detection limit with 3 times of signals with make an uproar
The concentration corresponding to ratio of sound is theoretical detection limit, with 10 times of signals with the concentration corresponding to the ratio of noise for theoretical quantitative limit.
According to calculated theoretical detection limit concentration and theoretical quantitative limit concentration, it is configured to machine on a series of standard working solution,
Actual detection limit concentration and actual quantification limit concentration is determined with practical situation.
The method 4-MEI and THI theory detection limit and theoretical quantitative limit concentration are respectively 0.001 μ g/mL, 0.003 μ g/
mL.It is configured to machine on the standard working solution of reality, determines that acceptable detection limit and quantitative limit concentration are divided according to practical situation
It is not 0.003 μ g/mL, 0.010 μ g/mL.So when being sampled as 1mg, after pre-treatment, final constant volume is to 1.0mL, obtains
Detection is limited to 3mg/kg, is quantitatively limited to 10mg/kg.
Sample recovery of standard addition measures:
Use the detection method of by-product 4-MEI and THI in the caramel color of the present invention, in caramel color, add three
The mixed standard solution of concentration level (being shown in Table 4,10mg/kg, 20mg/kg, 200mg/kg) 4-MEI and THI carries out mark-on recovery
Rate is tested, and experimental procedure is repeated 6 times with sample detection step, each concentration, the results are shown in Table 4, and the mark-on of 4-MEI and THI reclaims
Rate is respectively between 88.3～103.5% and 85.3～101.7%.
The accuracy experiment of table 4 method
The present invention detects the method for by-product 4-MEI and THI in caramel color and can efficiently separate for caramel color
Purifying, measurement result is 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 caramel color sample
In the accompanying drawings, abscissa is retention time (minute), and vertical coordinate is relative abundance.
Wherein in Fig. 1, Fig. 2
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)
Detailed description of the invention
Embodiment
(1) preparation of testing sample solution comprises the following specific steps that:
A () prepares Solid-Phase Extraction load solution: weigh caramel color sample 1g (accurately to 0.001g), is placed in 100mL and holds
In measuring bottle, add water and be settled to scale.Take 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), adds water and is settled to 2mL, treat Solid phase extraction after mixing.
B () solid-phase extraction column activates: selecting mixed type cation exchange solid-phase extraction column, substrate is polystyrene-diethyl
Alkenyl benzene high polymer, 60mg, 3mL, or quite person.Successively with 2mL methanol, the activation of 2mL water before using.
(c) Solid-Phase Extraction: the sample solution (a) prepared adds in the pillar just activated in (b), and coutroi velocity is little
In 0.5mL/min, draining, add 1mL water and 1mL methanol drip washing, coutroi velocity is less than 1.0mL/min, drains, uses eluent
(ammonia+methanol=5+95 (v/v)) 2mL eluting is collected, and coutroi velocity is less than 0.5mL/min, drains.Liquid will be collected less than 50
Under the conditions of DEG C, nitrogen dries up, residue 0.5mL solution (ammonia+acetonitrile+water=0.05+5+94.5 (v/v)) constant volume, and vortex mixes
Close 1min, cross 0.22 μm water system microporous filter membrane, i.e. prepare testing sample solution, inner mark method ration.
(2) sample detection comprises the following specific steps that:
A the preparation of () standard solution: the most accurately weigh 4-MEI, THI and D6-4-MEI standard substance, with water dissolution, divides
Not being made into the stock solution of 0.5mg/mL, 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).
Flowing phase: A is 0.05% ammonia spirit；B is acetonitrile.Condition of gradient elution is shown 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, cation
Ion spray voltage: cation 4000v
Volatile Gas temperature: 400 DEG C
Capillary temperature: 270 DEG C
Sheath gas: 60Arb
Auxiliary gas: 15Arb
Collision gas: argon
Scan pattern: multiple-reaction monitoring (MRM), each ion parameters refers to table 2
Measuring each compound quantitative daughter ion peak area, D6-4-MEI is internal standard, makees 4-MEI (THI) the most respectively with interior
Target peak area ratio 4-MEI (THI) concentration (ng/mL) standard curve, curvilinear equation is shown in formula (1):
Y=ax+b (1)
In formula: x 4-MEI or THI peak area and the ratio of internal standard material D6-4-MEI peak area；
The concentration of y 4-MEI or THI, unit is nanograms per milliliter (ng/mL).
In aforementioned manners any caramel color sample is detected, testing result such as table 5 below.
Table 5 sample detection result
Claims (1)
1. by-product 4-methylimidazole and a detection method for 2-acetyl group-4-hydroxy-butyl imidazoles, the party in caramel color
Method comprises the steps: the preparation of (1) testing sample solution；(2) sample detection；(3) interpretation of result, it is characterised in that its
The preparation of middle step (1) testing sample solution comprises the following specific steps that:
A () prepares Solid-Phase Extraction load solution: weigh caramel color sample 1g, accurately to 0.001g, is placed in 100mL volumetric flask
In, add water and be settled to scale, take the above-mentioned sample solution of 0.1mL, add the hydrochloric acid solution 0.1mL of 0.02moL/L, add 1.0 μ g/
The D6-4-MEI inner mark solution 0.2mL of mL, adds water and is settled to 2mL, treat Solid phase extraction after mixing；
B () solid-phase extraction column activates: selecting mixed type cation exchange solid-phase extraction column, substrate is polystyrene-divinyl base
Benzene high polymer, 60mg, 3mL, successively with 2mL methanol, the activation of 2mL water before using；
(c) Solid-Phase Extraction: the sample solution (a) prepared adds in the pillar just activated in (b), and coutroi velocity is less than
0.5mL/min, drains, and adds 1mL water and 1mL methanol drip washing, and coutroi velocity is less than 1.0mL/min, drains, uses eluent 2mL
Eluting is collected, and described eluent is ammonia+methanol=5+95, v/v, and coutroi velocity is less than 0.5mL/min, drains, will collect liquid
Under the conditions of less than 50 DEG C, nitrogen dries up, residue 0.5mL solution constant volume, and described solution is ammonia+acetonitrile+water=0.05+5+
94.95, v/v, vortex mixed 1min, cross 0.22 μm water system microporous filter membrane, i.e. prepare testing sample solution, inner mark method ration；
Step (2) sample detection comprises the following specific steps that:
The preparation of (a) standard solution: the most accurately weigh 4-methylimidazole (4-Methylimidazole, 4-MEI), 2-second
Acyl group-4-hydroxy-butyl imidazoles (2-acetyl-4-tetrahydroxy-butylimidazole, THI) and D6-4-methyl miaow
Azoles (D6-4-Methylimidazole, D6-4-MEI) standard substance, with water dissolution, are 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；
Flowing phase: A is 0.05% ammonia spirit；B is acetonitrile；Condition of gradient elution is: 0～5.0min, 95%A, 5%B, flow velocity
0.4mL/min；5.1min, 95%A, 5%B, flow velocity 0.4mL/min；10.0min, 60%A, 40%B, flow velocity 0.4mL/min；
10.1～12.0min, 95%A, 5%B, flow velocity 0.4mL/min；Column temperature: 30 DEG C；Sample size: 10 μ L；
Mass detector condition: ionization mode: H-ESI ionization, cation；Ion spray voltage: cation 4000v；Volatile Gas
Temperature: 400 DEG C；Capillary temperature: 270 DEG C；Sheath gas: 60Arb；Auxiliary gas: 15Arb；Collision gas: argon；Scan pattern: how anti-
Should monitor (MRM), each ion parameters is as follows:
；
Measuring quantitative daughter ion peak area, D6-4-MEI is internal standard, then makees 4-MEI peak area and internal standard material D6-4-MEI peak
The ratio of area is with the same THI of ratio of the standard curve of 4-MEI concentration, THI peak area and internal standard material D6-4-MEI peak area
The standard curve of concentration, curvilinear equation is shown in formula (1):
Y=ax+b (1)
In formula: x 4-MEI or THI peak area and the ratio of internal standard material D6-4-MEI peak area；
The concentration of y 4-MEI or THI, unit is nanograms per milliliter (ng/mL)；
Step (3) interpretation of result comprises the following specific steps that:
The mensuration of (a) sample solution: in sample to be tested solution the response value of 4-MEI or THI should in the standard curve range of linearity,
Exceed sample introduction analysis again after the range of linearity then should dilute；
B () qualitatively judges: measure sample and standard working solution according to above-mentioned condition, if the mass chromatography peak in sample retains
Time and standard working solution excursion are within ± 2.5%；In sample, two daughter ions of target compound is the richest
The relative abundance spending solution fairly standard with concentration is consistent, and relative abundance deviation permits less than the maximum of qualitative ion relative abundance
Permitted deviation, then be can determine whether sample exists target compound 4-MEI or THI；Described qualitative ion relative abundance maximum allowable
Deviation is:
The statement of (c) analysis result:
In sample the content of 4-MEI and THI press formula (2) calculate:
X=(C-C0)*V*103/m/106……………………………………(2)
In formula:
The content of 4-MEI or THI in X sample, unit is milligrams per kilogram (mg/kg)；
C is checked in the concentration of 4-MEI or THI in sample sample introduction liquid by standard curve, and unit is nanograms per milliliter (ng/mL)；
C0Being checked in the concentration of 4-MEI or THI in blank sample sample introduction liquid by standard curve, unit is nanograms per 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.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| 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 |
| 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 |
| 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 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0212049A3 (en) * | 1985-08-26 | 1988-03-09 | 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 |
-
2014
- 2014-05-21 CN CN201410213812.4A patent/CN104297399B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0212049A3 (en) * | 1985-08-26 | 1988-03-09 | 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 |
Non-Patent Citations (5)
| Title |
|---|
| Determination of 2-methylimidazole,4-methylimidazole and 2-acetyl-4-(1,2,3,4-tetrahydroxybutyl)imidazole in caramel colours and cola using LC/MS/MS;Claudia Schlee等;《Journal fo chromatography B》;20121023;第927卷;第223～226页 * |
| Reversed-phase high-performance liquid chromatographic/mass spectromectric method for separation of 4-methylimidazole and 2-acetyl-4-(1,2,3,4-tetrahydroxybutyl)imidazole at pg levels;Borivoj Klejdus等;《Analytica Chimica Acta》;20031231;第477卷;第49～58页 * |
| Solid-phase extraction of 4(5)-methylimidazole(4Mel) and 2-acetyl-4(5)-(1,2,3,4-tetrahydroxybutyl)-imidazole(THI) from foods and beverages with subsequent liquid chromatographic-electrospray mass spectrometric quantification;Borivoj Klejdus等;《Journal of separation science》;20060228;第29卷(第3期);第2.2节-第2.5节，表5 * |
| 高效液相色谱法测定焦糖色素中4-甲基咪唑;肖义夫等;《现代预防医学》;20051231;第32卷(第3期);第249～250页 * |
| 高效液相色谱法测定焦糖色素中的4-甲基咪唑;陈洪兴等;《中国调味品》;20060630(第6期);第53～56页 * |
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