CN106053695A - Method for detecting content of ethyl carbamate in soybean-flavor Baijiu - Google Patents
Method for detecting content of ethyl carbamate in soybean-flavor Baijiu Download PDFInfo
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- CN106053695A CN106053695A CN201610480539.0A CN201610480539A CN106053695A CN 106053695 A CN106053695 A CN 106053695A CN 201610480539 A CN201610480539 A CN 201610480539A CN 106053695 A CN106053695 A CN 106053695A
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- 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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- 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
- G01N2030/022—Column chromatography characterised by the kind of separation mechanism
- G01N2030/027—Liquid chromatography
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- 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
- G01N2030/8809—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86 analysis specially adapted for the sample
- G01N2030/884—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86 analysis specially adapted for the sample organic compounds
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Abstract
The invention discloses a method for detecting a content of ethyl carbamate in soybean-flavor Baijiu. The method comprises a sample preprocessing step and an LC-MS detection step, wherein in the sample preprocessing step, a sample is prepared by the following steps: sucking 1mL of sample, placing the sample into a 10mL bottle, adding 100 microliters of 1000 microgram/L ethyl carbamate inner marker, ensuring the volume to 10mL by using distilled water, uniformly mixing, filtering by a 0.22 micrometer organic filter membrane, and performing the LC-MS determination for filtrate; and in the LC-MS detection step, detecting the content of the ethyl carbamate in the filtrate by using a liquid chromatography-mass spectrometer. In the detection method, the sample is directly loaded onto a machine after being diluted by using the distilled water and then filtered by the microporous filter membrane, so that the preprocessing process of the sample is simplified, and the recovery rate of the method and the stability of a detection result are improved.
Description
Technical field
The invention belongs to analytical chemistry field, relate to the analysis detection of micro constitutent in Chinese liquor, specifically disclose fermented soya beans, salted or other wise odor type
The liquid chromatography-mass spectrography detection method of urethanes in Chinese liquor, this detection method can be saved in sample pretreatment process
The use of organic solution, simplifies the pretreatment process of sample, improves accuracy and the sensitivity of testing result.
Background technology
Urethanes (is called for short EC), is the natural materials produced in food fermentation and storage, is widely present in
In the fermented products such as fermented wine, Yoghurt, soy sauce.Urethanes has genetoxic and a carcinogenecity, 2007, international cancer
EC is formally classified as 2A class carcinogen (i.e. the mankind are potentially carcinogenic thing) by disease research institution (IARC).
At present both at home and abroad the existing standard method about EC detection mainly have AOAC Official Method 994.7,
SN/T0285-2012 (inspection and quarantining for import/export industry standard) and GB5009.223-2014 (national food safety standard).Press
Detection method is divided, and mainly has gaschromatographic mass spectrometry external standard method, gaschromatographic mass spectrometry internal standard method and liquid chromatograph fluorescence method.Gas phase
For chromatographic mass spectrometry internal standard method is relative to gaschromatographic mass spectrometry external standard method, accuracy and the stability of method increase, but gas
All there is the problems such as pre-treatment length loaded down with trivial details, time-consuming, reagent loss be big in phase chromatographic mass spectrometry method.Liquid chromatograph fluorescence method is simple to operate,
Quickly, but accuracy and quantitatively the most bad.
Summary of the invention
The invention discloses the detection method of ethyl carbamate content in a kind of soybean-flavor liquor, the method is by simplifying
The pretreatment process of sample, can carry out quantitative analysis to the trace urethanes in soybean-flavor liquor fast and accurately,
Reduce testing cost, saved the detection time, improve the response rate of detection method and the stability of testing result.
In soybean-flavor liquor disclosed by the invention, the detection method of ethyl carbamate content comprises the following steps:
(1) measure the Wine Sample of certain volume, add certain density internal standard substance butyl carbamate, fixed with distilled water
Hold, filter membrane.
(2) take machine (liquid chromatograph-mass spectrometer) in the sample direct injected after filtration, select protonated amino Ethyl formate
Molecular ion 89.9m/z, butyl carbamate molecular ion 118m/z are that quota ion detects, after standard curve calculates
Obtain the content of urethanes in sample.
(3) liquid phase chromatogram condition:
Chromatographic column: Poroshell 120EC-C18,3.0 × 50mm, 2.7-micron；
Flowing phase: A phase is 0.1% (v/v) acetic acid aqueous solution, and B phase is acetonitrile；
Flow velocity: 0.25mL/min；
Gradient elution program: 0min, 95%A, 5%B；
1min, 90%A, 10%B；
2.5min, 15%A, 85%B；
2.8min, 95%A, 5%B；
(running time: 7.2min afterwards)
Column temperature: 40 DEG C；
Sample size: 10 μ L.
(4) Mass Spectrometry Conditions:
Ion source: electric spray ion source；
Scan mode: cation scans；
Detection mode: multiple-reaction monitoring；
Capillary voltage: 3100V；
Ion source temperature: 350 DEG C；
Flow velocity: 10.8L/min；
The qualitative ion of urethanes: 89.9m/z；62.2m/z；
The qualitative ion of butyl carbamate: 118m/z；62.2m/z.
The technique effect that the present invention is the most useful:
(1) sample pre-treatments is simple, it is not necessary to uses organic solvent, pollutes little.Before being below various conventional detection method
Process comparison:
Gaschromatographic mass spectrometry external standard method (SN/T 0285-2012): sample, after dichloromethane extraction, water-bath concentrate, uses second
Nitrile dissolves, and the most also needs to carry out normal hexane purification, PSA extraction；
Gaschromatographic mass spectrometry internal standard method (GB5009.223-2014): sample, after alkalescence kieselguhr Solid-Phase Extraction, takes off
Water, nitrogen blow concentration, after with methanol redissolve solve；
Liquid chromatograph fluorescence method: sample need to carry out derivation with accounting for an alcoholic solution-hydrochloric acid solution；
Detection method disclosed by the invention: distilled water diluting, filtering with microporous membrane.
(2) the upper machine testing time is short, and efficiency is high.It is below the sample detection Time transfer receiver of various conventional detection method:
Gaschromatographic mass spectrometry external standard method (SN/T 0285-2012): 51 minutes；
Gaschromatographic mass spectrometry internal standard method (GB5009.223-2014): 40 minutes；
Liquid chromatograph fluorescence method: 30 minutes；
Detection method disclosed by the invention: 10 minutes.
(3) method is highly sensitive, and detection limit is low.It is below the minimum quantitative detection limit comparison of various conventional detection method:
Gaschromatographic mass spectrometry external standard method (SN/T 0285-2012): 10 μ g/kg；
Gaschromatographic mass spectrometry internal standard method (GB5009.223-2014): 2.0 μ g/kg；
Liquid chromatograph fluorescence method: 5.0 μ g/L；
Detection method disclosed by the invention: 0.75 μ g/L.
(4) method stability and repeatability are preferably.
Owing to, in detection method disclosed by the invention, sample has only to use distilled water diluting constant volume, filter membrane, is i.e. available on the machine
Detection, reduces sample loss in extraction process and destruction, farthest ensure that the integrity of sample, the side of improve
The response rate of method.Method pretreatment process simply, easily operate, the most therefore improves stability and the repeatability of method.
Below in conjunction with specification drawings and specific embodiments, detection method and the Detection results of the present invention are carried out in detail
Explanation.
Accompanying drawing explanation
Fig. 1: EC concentration is the canonical plotting of 1～50 μ g/L；
Fig. 2: concentration is the urethanes of 10 μ g/L, butyl carbamate standard substance extract ion profile figure；
Fig. 3: in sample, urethanes extracts ion profile figure.
Detailed description of the invention
1, the preparation of standard solution
Urethanes storing solution (100 μ g/mL): accurately weigh 10mg urethanes standard substance, molten with methanol
Solve, be settled to 100mL, be placed in 4 DEG C of refrigerators preservation.
Butyl carbamate storing solution (100 μ g/mL): accurately weigh 10mg butyl carbamate standard substance, molten with methanol
Solve, be settled to 100mL, be placed in 4 DEG C of refrigerators preservation.
Urethanes intermediate liquid (1000 μ g/L): accurately draw urethanes storing solution (100 μ g/mL) 1mL,
It is settled to 100mL with methanol-water (1:9v/v) solution, 4 DEG C of refrigerators preserve.
Butyl carbamate intermediate liquid (1000 μ g/L): accurately draw butyl carbamate storing solution (100 μ g/mL) 1mL,
It is settled to 100mL with methanol-water (1:9v/v) solution, 4 DEG C of refrigerators preserve.
Standard curve working solution: respectively draw urethanes intermediate liquid (1000 μ g/L) 10 μ L, 20 μ L, 50 μ L,
100 μ L, 200 μ L, 500 μ L are in 6 10mL volumetric flasks, then are separately added into butyl carbamate intermediate liquid (1000 μ g/L) 100 μ
L, is settled to scale with distilled water, obtains 1 μ g/L, 2 μ g/L, 5 μ g/L, 10 μ g/L, 20 μ g/L, 50 μ g/L, internal standard carbamic acid
Butyl ester is the standard curve working solution of 10 μ g/L, now with the current.
2, the pre-treatment of sample
Draw 1mL sample to be placed in 10mL volumetric flask, add the butyl carbamate internal standard of 100 μ L 1000 μ g/L, with steaming
Distilled water is settled to 10mL, mixing, and through the 0.22 organic membrane filtration of μm, filtrate measures for LC-MS.
3, liquid chromatography-mass spectrography detection
(1) liquid phase chromatogram condition:
Chromatographic column: Poroshell 120EC-C18,3.0 × 50mm, 2.7-micron；
Flowing phase: A phase is 0.1% (v/v) acetic acid aqueous solution, and B phase is acetonitrile；
Flow velocity: 0.25mL/min；
Gradient elution program: 0min, 95%A, 5%B；
1min, 90%A, 10%B；
2.5min, 15%A, 85%B；
2.8min, 95%A, 5%B；
(running time: 7.2min afterwards)
Column temperature: 40 DEG C；
Sample size: 10 μ L.
(2) Mass Spectrometry Conditions:
Ion source: electric spray ion source；
Scan mode: cation scans；
Detection mode: multiple-reaction monitoring；
Capillary voltage: 3100V；
Ion source temperature: 350 DEG C；
Flow velocity: 10.8L/min；
The qualitative ion of urethanes: 89.9m/z；62.2m/z；
The qualitative ion of butyl carbamate: 118m/z；62.2m/z；
(3) making of standard curve
By concentration be 1 μ g/L, 2 μ g/L, 5 μ g/L, 10 μ g/L, 20 μ g/L, the standard curve working solution of 50 μ g/L (include
The internal standard of 10 μ g/L butyl carbamates) carry out liquid chromatography-mass spectrometry detection.With ethyl carbamate concentration as abscissa, ammonia
The peak area of base Ethyl formate is vertical coordinate with the ratio of the peak area of butyl carbamate, draws such as the standard curve of Fig. 1.To mark
Directrix curve carries out linear regression analysis, obtains the regression equation of standard curve: y=2.274555x-0.004084, can by Fig. 1
Know, this method linearly dependent coefficient R in 1～50 μ g/L concentration ranges2=0.9993.
(4) detection of sample solution
Under the test condition equal with standard curve working solution, sample solution is carried out liquid chromatography-mass spectrometry detection,
The content of urethanes in sample solution is obtained further according to target peak area and standard curve.
4, the minimum detectability of method and minimum quantitative limit
Detection is limited to analysis method and can detect least concentration or the minimum flow of tested component at the specified experimental conditions,
When being typically 3:1 with signal to noise ratio (S/N), the amount of corresponding concentration or injection instrument determines detection limit.It is 3 reckonings according to S/N, this
The minimum detectability of inventive method is (LOD) 0.20 μ g/L.
Quantitatively it is limited to the minimum flow that in sample, measured object can be quantitatively determined, is typically 10:1 phase with signal to noise ratio (S/N)
The concentration answered or the amount injecting instrument determine quantitative limit.It is 10 reckonings according to S/N, the minimum quantitative limit (LOQ) of the inventive method
It is 0.75 μ g/L.
5, the precision of method and stability
In the inventive method, take 6 parts of identical samples, after identical sample pre-treatments, working with standard curve
Under the test condition that solution is equal, sample solution is carried out liquid chromatography-mass spectrometry detection, and to the urethanes in sample
Carry out quantitative Analysis.The precision of method is obtained by the relative standard deviation (RSD) calculating testing result, the inventive method
Precision is 3.49%, good stability.
6, the substrate recovery of standard addition of method and sample recovery of standard addition
In the inventive method, taking 2 parts of identical blank samples, a copy of it adds quantitative ingredient standard substance to be measured.3
Part sample (blank sample, mark-on sample, quantitative criterion material) simultaneously by identical analytical procedure analysis detection, blank sample with
The testing result difference of mark-on sample is the substrate recovery of standard addition of method divided by the testing result of quantitative criterion material, this
The substrate recovery of standard addition of bright method is 95～105%.
In the inventive method, taking 2 parts of identical known samples containing composition to be measured, a copy of it adds quantitative to be measured
Ingredient standard substance.3 parts of samples (sample, mark-on sample, quantitative criterion material) are detected by identical analytical procedure analysis simultaneously,
The testing result difference of 2 parts of samples is the sample recovery of standard addition of method divided by the testing result of quantitative criterion material, this
The sample recovery of standard addition of bright method is 92～99%.
The substrate recovery of standard addition of the inventive method and sample recovery of standard addition can meet the testing requirement of national standard.
Claims (4)
1. a detection method for ethyl carbamate content in soybean-flavor liquor, including:
The pre-treatment step of sample, measures the Wine Sample of certain volume, adds certain density internal standard substance butyl carbamate,
Using distilled water constant volume, filter membrane, filtrate measures for LC-MS；
Liquid chromatograph-mass spectrometer detecting step, machine in filtrate direct injected, select protonated amino Ethyl formate molecular ion
89.9m/z, butyl carbamate molecular ion 118m/z are that quota ion detects, and obtain sample after standard curve calculates
The content of middle urethanes.
The detection method of ethyl carbamate content in soybean-flavor liquor the most according to claim 1, it is characterised in that: institute
State and the pre-treatment step of sample is prepared sample as follows: draw 1mL sample and be placed in 10mL volumetric flask, add 100 μ
The butyl carbamate internal standard of L1000 μ g/L, is settled to 10mL with distilled water, and mixing, through the 0.22 organic membrane filtration of μm.
The detection method of ethyl carbamate content in soybean-flavor liquor the most according to claim 1, it is characterised in that: institute
Stating in liquid chromatograph-mass spectrometer detecting step, liquid phase chromatogram condition is:
Chromatographic column: Poroshell 120EC-C18,3.0 × 50mm, 2.7-micron；
Flowing phase: A phase is 0.1%v/v acetic acid aqueous solution, and B phase is acetonitrile；
Flow velocity: 0.25mL/min；
Gradient elution program: 0min, 95%A, 5%B；
1min, 90%A, 10%B；
2.5min, 15%A, 85%B；
2.8min, 95%A, 5%B；
Rear operation time: 7.2min；
Column temperature: 40 DEG C；
Sample size: 10 μ L.
The detection method of ethyl carbamate content in soybean-flavor liquor the most according to claim 1, it is characterised in that: institute
Stating in liquid chromatograph-mass spectrometer detecting step, Mass Spectrometry Conditions is:
Ion source: electric spray ion source；
Scan mode: cation scans；
Detection mode: multiple-reaction monitoring；
Capillary voltage: 3100V；
Ion source temperature: 350 DEG C；
Flow velocity: 10.8L/min；
The qualitative ion of urethanes: 89.9m/z；62.2m/z；
The qualitative ion of butyl carbamate: 118m/z；62.2m/z.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107037164A (en) * | 2017-05-25 | 2017-08-11 | 安徽古井贡酒股份有限公司 | A kind of method of urethanes in quick detection white wine |
| CN110108820A (en) * | 2019-06-13 | 2019-08-09 | 广东省生物工程研究所（广州甘蔗糖业研究所） | The measuring method of ethyl carbamate content in a kind of Yoghourt |
| CN113295797A (en) * | 2021-05-26 | 2021-08-24 | 陕西科技大学 | Method for rapidly detecting ethyl carbamate in white spirit based on ultra-high performance liquid chromatography combined high-resolution mass spectrometry |
| CN114441521A (en) * | 2022-01-27 | 2022-05-06 | 宜宾五粮液股份有限公司 | Preparation method of white spirit ethyl carbamate quick-detection test paper |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107037164A (en) * | 2017-05-25 | 2017-08-11 | 安徽古井贡酒股份有限公司 | A kind of method of urethanes in quick detection white wine |
| CN110108820A (en) * | 2019-06-13 | 2019-08-09 | 广东省生物工程研究所（广州甘蔗糖业研究所） | The measuring method of ethyl carbamate content in a kind of Yoghourt |
| CN113295797A (en) * | 2021-05-26 | 2021-08-24 | 陕西科技大学 | Method for rapidly detecting ethyl carbamate in white spirit based on ultra-high performance liquid chromatography combined high-resolution mass spectrometry |
| CN114441521A (en) * | 2022-01-27 | 2022-05-06 | 宜宾五粮液股份有限公司 | Preparation method of white spirit ethyl carbamate quick-detection test paper |
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Application publication date: 20161026 |