CN104655753B - The assay method of 3-acetyl group-2,5-thioxene in a kind of food additive - Google Patents

The assay method of 3-acetyl group-2,5-thioxene in a kind of food additive Download PDF

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CN104655753B
CN104655753B CN201510069074.5A CN201510069074A CN104655753B CN 104655753 B CN104655753 B CN 104655753B CN 201510069074 A CN201510069074 A CN 201510069074A CN 104655753 B CN104655753 B CN 104655753B
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acetyl
thioxene
food additive
internal standard
standard substance
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CN104655753A (en
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徐雪芹
李小兰
贾海江
田兆福
陈志燕
周芸
黄善松
许蔼飞
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China Tobacco Guangxi Industrial Co Ltd
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China Tobacco Guangxi Industrial Co Ltd
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Abstract

The present invention relates to 3 acetyl group 2 in a kind of food additive; the assay method of 5 thioxenes; select containing interior target normal hexane ultrasonic extraction sample; it is directly entered gas chromatograph-mass spectrometer after extract filter membrane to be measured; using selected ion monitoring (SIM) mode detection, internal standard method is carried out quantitatively.This method uses Gas-phase acidity to measure 3 acetyl group 2 in food additive; 5 thioxenes; SIM scan mode is used can effectively to eliminate complicated substrate interference; there is pre-treatment simple, easily operated; selectivity is good, the repeated feature such as high, the most accurate; it is suitable for qualitative confirmation and the quantitative determination of 3 acetyl group 2,5 thioxenes in food additive.

Description

The assay method of 3-acetyl group-2,5-thioxene in a kind of food additive
Technical field
The invention belongs to food additive physical and chemical inspection technical field, be specifically related to 3-acetyl in a kind of food additive The assay method of base-2,5-thioxene.
Background technology
Food additive is of a great variety, form of diverse, and existence form has solid-state, liquid, paste etc., and additive types is different Solubization also has the biggest difference, is even insoluble in ethanol.Along with public's growing interest to food safety, particularly food adds Agent is closely related with daily life, and for making taste of food delicious, various kinds of foods is added with food additive the most to some extent Adding agent, apply quite varied, its quality and safety problem are with becoming the focus of public concern, and literature survey shows: European Union is Forbid being used in food additive 3-acetyl group-2,5-thioxene as edible essence.On June 4th, 2013, Europe was eaten Product safety management office (EFSA) disclose 3-acetyl group-2, the suggestion that 5-thioxene reappraises, it is believed that this material exists Internal and in vitro tests all shows mutagenicity, uses as food spice and there is safety problem.On June 14th, 2013, EU Committee by regulation (Regulation(EC)No 545/2013), forbid 2,5-dimethyl-3-acetyl group-thiophene is made Use for food spice, it is deleted with spice regulation annex I food spice inventory from food.On August 14th, 2014, Essence scenting cosmetics TIA of China is main to Some Domestic spices and essence according to existing security evaluation conclusion and association Manufacturing enterprise's " 3-acetyl group-2,5-thioxene " produces and the survey result of service condition, has issued spices and essence industry Self-discipline file-and about 3-acetyl group-2, the restriction of 5-thioxene requires (sweetening treatment association word [2013] 62), self-discipline file rule Fixed: from this self-discipline file distribution, production of flavor enterprise must not produce 3-acetyl group-2 as food spice, 5-bis- Methylthiophene;Essence for food manufacturing enterprise adjusts formula, must not re-use this material.
China there is no 3-acetyl group-2 in food additive, the detection method of 5-thioxene at present, also lacks relevant The research of aspect, for guaranteeing the safety of food additive, set up one can quickly, in easy, batch quantity analysis food additive The method of 3-acetyl group-2,5-thioxene content is of great practical significance.
Summary of the invention
Goal of the invention: provide one can quickly, easy, accurate 3-acetyl group-2,5-diformazan in analysis food additive The gas chromatography-mass spectrography detection method of base thiophene, fills up the blank of this materials analysis methods.Pre-treatment of the present invention is simple, Easily operated, qualitative accurately, sensitivity and the response rate are high.
The technical scheme is that and the mensuration side of 3-acetyl group-2,5-thioxene in a kind of food additive is provided Method, it is characterised in that comprise the following steps:
1) weigh a certain amount of food additive sample, join in the n-hexane extract containing internal standard substance, ultrasonic extraction Take, stand, take supernatant through membrane filtration.
2) filtrate uses gas chromatograph-mass spectrometer to detect, and choice ion pattern detects, by component peaks area and internal standard The ratio of peak area carries out inner mark method ration.
Described ultrasonic time is 15-30min, time of repose 1-3min.
Described internal standard substance is ethyl oxalate, and in described n-hexane extract, internal standard substance concentration is 5 μm ol/L.
Described filter membrane is organic filter membrane, and aperture is 0.22 μm or 0.45 μm.
The GC conditions of described method: use Thermo TG-WAXMS chromatographic column to separate, injector temperature 220 DEG C, sample size 1 μ L, split ratio 1:10, post flow: 1mL/min, heating schedule: 50 DEG C keep 1min, with 20 DEG C/min liter To 200 DEG C, keep 20min.
Described Mass Spectrometry Conditions: use electron ionization sources, voltage of power 70eV, ion source temperature 300 DEG C;Level Four bar temperature 280 DEG C, solvent delay: 7.5min, select ion (SIM) detection scanning quantitation, 3-acetyl group-2,5-thioxene and internal standard Thing ethyl oxalate qualitatively and quantitatively selects ion such as following table:
Sequence number Compound name Retention time (min) Qualitative ion and kurtosis ratio thereof Quota ion
1 3-acetyl group-2,5-diformazan 8.36 139.154.111(100:55:25) 139
Base thiophene
2 Ethyl oxalate 13.59 74:45:30(100:93:67) 74
Beneficial effects of the present invention is as follows:
1, the present invention uses gas chromatogram to separate first, mass spectrum selects ion scan monitoring, the mode of inner mark method ration to examine Surveying 3-acetyl group-2 in food additive, the content of 5-thioxene, this method is the shortest, and sensitivity and the response rate are high, weight Renaturation is good, can realize quick to this material in food additive, accurate, batch detection.
2, the present invention uses SIM scan mode can effectively eliminate complicated substrate interference.
3, the present invention is easy and simple to handle, quick, accurate, sensitivity and reproducible advantage.
4, chromatographic condition of the present invention makes object separate preferably with the chromatographic peak of internal standard substance, and has preferably Linear dependence, detection be limited to 1.02mg/kg.
Accompanying drawing explanation
Accompanying drawing 1 measures program for the inventive method.
Accompanying drawing 2 is the sample chromatogram figure of present example 1
Detailed description of the invention
Below in conjunction with the accompanying drawings the detailed description of the invention of the present invention is described in further detail.
Embodiment 1
1, instrument and reagent:
Gas chromatograph-mass spectrometer (GC-MS) (Thermo TRACE 1300) chromatographic column (Thermo TG-WAXMS, 30m × 0.25mm × 0.25 μm), Millipore Q-pod Element ultrapure water system (Millipore company of the U.S.);AB204-S Type electronic analytical balance (sensibility reciprocal 0.0001g) (Mei Tele company of Switzerland), 0.22 μm micropore filtering film, ultrasonic cleaner.
Ultra-pure water (18M Ω), ethanol (chromatographically pure, lark prestige chemical reagents corporation), 250pmoL/ μ L, Agilent company).
2, solution preparation
(1) inner mark solution preparation
Internal standard storing solution: accurately weigh 0.0365g (being accurate to 0.0001g) ethyl oxalate in 50mL volumetric flask, uses N-hexane dissolution constant volume, obtain the internal standard mother solution of 0.73g/L.Preserve in shady and cool, the place of being dried, prevent from making moist.
Internal standard extract: pipette 1mL internal standard storing solution in 1000mL volumetric flask, be settled to scale with normal hexane, obtain dense Degree is the extract of 5 μm ol/L, preserves in shady and cool, the place of being dried.
(2) standard working solution preparation: accurately pipette the 3-acetyl group-2,5-dimethyl that 0.1002g purity is 99.8% Thiophene standard solution, in 100ml volumetric flask, with internal standard extract constant volume, obtains 3-acetyl group-2,5-thioxene mother solution.Point Not pipetting the mother solution of different volumes, being formulated as concentration with internal standard extract is 0.1mg/L, 0.5mg/L 1.0mg/L 2.0mg/L Six grades of series standard solution of 5.0mg/L 10.0mg/L.
(3) gas chromatography/mass spectrometry condition
Chromatographic condition: use Thermo TG-WAXMS chromatographic column to separate, injector temperature 220 DEG C, sample size 1 μ L, Split ratio 1:10, post flow: 1mL/min, heating schedule: 50 DEG C keep 1min, rise to 200 DEG C with 20 DEG C/min, keep 20min;
Mass Spectrometry Conditions: use electron ionization sources, voltage of power 70eV, ion source temperature 300 DEG C;Level Four bar temperature 280 DEG C, Solvent delay: 7.5min, selects ion detection scanning quantitation, 3-acetyl group-2,5-thioxene and internal standard substance oxalic acid diethyl Ester qualitatively and quantitatively selects ion such as following table:
(4) Specification Curve of Increasing: the standard solution of different series concentration is entered gas chromatograph-mass spectrometer (GC-MS) detection; With the peak area of measured object with its in the ratio (Y) of target peak area the concentration (X) of measured object is carried out linear regression, try to achieve 3- The standard curve of acetyl group-2,5-thioxene.
(5) sample preparation and analysis: accurately weigh 0.3g testing sample, put in 50ml ground triangular flask, accurately add 25mL internal standard extract (ethyl oxalate concentration is 5 μm ol/L), ultrasonic 15-30min, sways conical flask and makes it a moment after taking-up Mix homogeneously, stands, takes supernatant through the laggard row gas chromatograph-mass spectrometer (GC-MS) analysis of 0.22 μm membrane filtration.
The different manufacturers chosen in the present embodiment, 58 samples of different types of food additive, have 2 samples Detect containing 3-acetyl group-2,5-thioxene, content be respectively 37.6mg/kg (sample state is liquid) and 102.3mg/kg (sample state is extractum).
Embodiment 2
The recovery of standard addition of the present invention is detected by the present embodiment, analyzes method as follows:
So that in embodiment 1, detection is containing 3-acetyl group-2, the sample of 5-thioxene is object, with reference to embodiment 1 Method, uses basic, normal, high three levels to add calibration method, addition 3-acetyl group-2 in sample, 5-thioxene standard specimen, Survey content after its mark-on.Each horizontal parallel measures three times, averages and carries out the calculating of recovery of standard addition, measurement result table 1:
Table 1 method recovery of standard addition
As known from Table 1, the recovery of standard addition of sample, between 94.88-100.52%, illustrates the response rate of this method relatively Good.
Embodiment 3
The precision of the present invention is detected by the present embodiment, analyzes method as follows:
So that in embodiment 1, detection is containing 3-acetyl group-2, the sample of 5-thioxene is object, with reference to embodiment 1 Method, 3-acetyl group-2 in 6 parallel assay mark-on samples, the content of 5-thioxene, calculate relative standard deviation, investigate The precision of method, result is as shown in table 2,
The precision of table 2 method
From table 2 it can be seen that relative standard deviation RSD of this method is less than 3%, the reproducible of this method is described, full Foot requirement of experiment.
The above embodiment of the present invention only clearly demonstrates example of the present invention, and is not the reality to the present invention Execute the restriction of mode, for those of ordinary skill in the field, can also be made other on the basis of the above description The change of multi-form or variation, cannot give exhaustive to embodiment used here, every belongs to technical solution of the present invention That is amplified out obviously changes or changes the row still in protection scope of the present invention.

Claims (1)

1. 3-acetyl group-2 in a food additive, the assay method of 5-thioxene, it is characterised in that include following step Rapid: to weigh a certain amount of food additive sample, join in the n-hexane extract containing internal standard substance, after ultrasonic extraction, quiet Putting, take supernatant membrane filtration, filtrate gas chromatograph-mass spectrometer (GC-MS), choice ion pattern-inner mark method ration measures food The content of 3-acetyl group-2,5-thioxene in product additive;
The described ultrasonic extraction time is 15-30min, and described time of repose is 1-3min;
Described internal standard substance is ethyl oxalate;
In described n-hexane extract, internal standard substance concentration is 5 μm ol/L;
Described filter membrane is organic filter membrane, and aperture is 0.22 μm or 0.45 μm;
Chromatographic condition in described step is as follows:
Chromatographic column: use Thermo TG-WAXMS chromatographic column to separate
Injector temperature: 220 DEG C
Sample size: 1 μ L
Split ratio: 1:10
Post flow: 1mL/min
Heating schedule: 50 DEG C keep 1min, rise to 200 DEG C with 20 DEG C/min, keep 20min;
Mass Spectrometry Conditions in described step is as follows:
Ion source: electron ionization sources
Voltage of power: 70eV
Ion source temperature: 300 DEG C
Level Four bar temperature 280 DEG C
Solvent delay: 7.5min,
Scan mode: select ion detection scanning quantitation;
3-acetyl group-2,5-thioxene and internal standard substance ethyl oxalate qualitatively and quantitatively select ion such as following table:
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CN106442776B (en) * 2016-09-13 2019-05-14 华南理工大学 A method of measurement acetyl content
CN107064358B (en) * 2017-04-14 2020-01-17 广西中烟工业有限责任公司 Method for detecting 3-acetyl-2,5-dimethylthiophene by combining magnetic solid-phase extraction with high performance liquid chromatography
CN107192772B (en) * 2017-05-05 2020-01-17 广西中烟工业有限责任公司 Method for detecting 3-acetyl-2,5-dimethylthiophene
CN107144656B (en) * 2017-05-27 2020-03-31 浙江省食品药品检验研究院 Method for measuring 3-acetyl-2, 5-dimethyl thiophene in edible essence by GC-MS/MS (gas chromatography-Mass Spectrometry/Mass Spectrometry)
CN110221000A (en) * 2019-07-10 2019-09-10 山东省食品药品检验研究院 A kind of method of 3- acetyl group -2,5- thioxene in detection food

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