CN104655776A

CN104655776A - Method for detecting acid light yellow G in paper packaging material for foods

Info

Publication number: CN104655776A
Application number: CN201510069265.1A
Authority: CN
Inventors: 徐雪芹; 田兆福; 李小兰; 陈志燕; 贾海江; 蒋宏霖
Original assignee: China Tobacco Guangxi Industrial Co Ltd
Current assignee: China Tobacco Guangxi Industrial Co Ltd
Priority date: 2015-02-10
Filing date: 2015-02-10
Publication date: 2015-05-27
Anticipated expiration: 2035-02-10
Also published as: CN104655776B

Abstract

The invention relates to a method for detecting acid light yellow G in a paper packaging material for foods. The method comprises the steps of carrying out ultrasonic extraction on a sample by using an ethanol, 0.1% acetic acid and a water solution which are in the volume ratio of 1:3:6; and directly entering an ultra-high performance liquid chromatography and quadrupole rod mass spectrum (UPLC-MS) combined instrument to detect after treating by using a filtering membrane. The method is simple in pretreatment and can be used for rapidly and accurately detecting the content of the acid light yellow G in the paper packaging material for foods. According to the method, retention time of chromatography and simultaneous qualitation of mass spectrum are adopted, and therefore, compared with the traditional liquid chromatographic detecting method, the method has the advantages that the defect of easily-caused false positive is overcome, a result is accurate and reliable, and the selectivity and repeatability are good. No poisonous and harmful chemical products are used in the experimental process, so that few hazards for operating staffs are generated, and the method is easy to operate. An optimized gradient elution program is adopted according to the feature that a matrix of the paper packaging material for foods is complex, so that interferences are eliminated, the recovery rate is high, and the detected result is accurate.

Description

The assay method of Acid Light Yellow G in a kind of paper food packaging materials

Technical field

The invention belongs to physical and chemical inspection technical field, be specifically related to the assay method of Acid Light Yellow G content in paper food packaging materials.

Background technology

In recent years, the quality influence of the paper wrapper of direct food contact the safety of food, pattern exquisite and bright-coloured on wrappage, often containing prohibitive dye, because forbidding pigment is cheap, coloring stabilized, many businessman are applied to packaging material for food for reducing costs, Acid Light Yellow G belongs to the acid industrial dye of azo, be difficult to biodegradation, environmental pollution is larger, European Union forbade using in textile before 10 years, paper wrapper is bright-colored, multiple inks printing is often had to form, if containing this material in packaging material for food, it migrates in food from wrapping paper, all the aromatic amine compounds with carcinogenicity can be resolved into by bacterium in enteron aisle and reductase in human body, long-term edible very large to harm.There is no detection document and the analytical approach of Acid Light Yellow G in papery food material at present, the research therefore adding intensity detection method and standard is imperative, is necessary that the method for a kind of simple and fast of suggestion carries out Safety monitoring to it.

Summary of the invention

The present invention overcomes the deficiencies in the prior art, the assay method of Acid Light Yellow G content in a kind of new paper food packaging materials is provided, adopt the ultrasonic extraction of alcohol, acetic acid aqueous solution, directly enter Ultra Performance Liquid Chromatography-quadrupole rod GC-MS after filtering membrane to detect, realize the tested azo dyes of accurate quantitative analysis.

Technical scheme of the present invention is to provide the assay method of Acid Light Yellow G content in a kind of paper food packaging materials, it is characterized in that comprising the following steps:

(1) preparation of extract: get 1.01mL purity be the acetic acid of 99.8% in 1L volumetric flask, use ultrapure water constant volume, be mixed with the acetic acid solution that concentration is 0.1%; Accurately measure ethanol 100mL, 0.1% acetic acid solution 300mL in 1L volumetric flask, use ultrapure water constant volume, mixing after for subsequent use.

(2) standard working curve makes: the standard solution with ethanol, Acid Light Yellow G storing solution being made into different series concentration, carries out efficient liquid phase-tandem mass spectrum and detects; Then carry out linear regression with the concentration (X) of ratio (Y) to measured object of the peak area of measured object and its outer target peak area, try to achieve the typical curve of Acid Light Yellow G;

(3) sample preparation and analysis: accurately take 1.0g paper food packaging materials sample to be measured, put into 50ml ground triangular flask, accurately add 30mL ethanol: 0.1% acetic acid: aqueous solution (1:3:6), ultrasonic 15min, 5min is left standstill after taking out, get supernatant, through 0.22 μm of organic membrane filtration laggard enter Ultra Performance Liquid Chromatography-quadrupole rod GC-MS analyze;

Chromatographic separation condition: chromatographic column: AgilentC18 (4.6 × 150mm, 5 μm); Flow velocity: 0.5mL/min; Column temperature: 30 DEG C; Sample size: 5 μ L; Mobile phase A: acetonitrile, Mobile phase B: 0.01mol/L ammonium acetate, gradient elution.

Mass Spectrometry Conditions: ion gun: negative ion (ESI-) type collection; Electron spray voltage :-4500V (ESI-), 5000V (ESI+); Ion source temperature: 550 DEG C; Assisted gas Gas1 pressure: 60psi; Detection mode: multiple-reaction monitoring mode monitoring, analyze the quota ion of thing to, qualitative ion pair, go a bunch voltage (DP) and collision energy (CE) to see the following form 1:

Table 1 quota ion of analyzing thing to, qualitative ion pair, remove a bunch voltage (DP) and collision energy (CE)

Compared with prior art, beneficial effect of the present invention is: the mensuration being suitable for Acid Light Yellow G in paper food packaging materials, quick, the accurate content detecting Acid Light Yellow G in paper food packaging materials of the method energy, the process that measures is disturbed less, and testing result is accurate.

Method of the present invention overcomes the deficiency of prior art sample treatment, for the Matrix optimization eluent gradient program of paper food packaging materials sample, simplifies sample pre-treatments.Compared with prior art the present invention has following effect:

1, compared with traditional detection method, UPLC-MS system significantly improves the accuracy of the repeatability of quantitative test, reliability and qualitative analysis, and overcome and only use the false-positive shortcoming of the qualitative easy generation of chromatographic retention, this method result accurately and reliably, selectivity is good, can realize accurate quantitative analysis.

2, the ammonium acetate mobile phase of 0.01mol/L is adopted to eliminate interference.

3, adopt the gradient elution program optimized, the recovery is high, and measurement result is accurate.

4, this method has easy and simple to handle, quick, accurate, sensitivity and reproducible advantage.

Accompanying drawing explanation

Fig. 1 is the mensuration program of the inventive method;

Fig. 2 is the chromatogram of Acid Light Yellow G standard items;

Fig. 3 is Acid Light Yellow G chromatogram in sample;

Embodiment

For ease of better understanding the present invention, the present invention further illustrates in conjunction with specific embodiments.

Embodiment 1

Instrument of the present invention and reagent, material

U.S. Agilent1290/6460 Ultra Performance Liquid Chromatography-quadrupole rod GC-MS; Chromatographic column: AgilentC18 (4.6 × 150mm, 5 μm), 0.22 μm of micropore filtering film, ultrasonic cleaning machine.

Ultrapure water (18M Ω), acetonitrile (chromatographically pure, lark prestige chemical reagents corporation), it is pure that ethanol, acetic acid and ammonium acetate are top grade.

Standard working curve makes: with ethanol, Acid Light Yellow G standard reserving solution is made into 0.5,1.0,5.0,10,20,40 μ g/L series concentration, production standard curve.

Sample pre-treatments: take 1.0g sample (being accurate to 0.0001g), be placed in 50ml ground triangular flask, accurately add 30mL extract solution (1:3:6), sonic oscillation 15min, solution direct injected after 0.22 μm of organic membrane filtration after extraction.

Liquid chromatography and Mass Spectrometry Conditions

Liquid phase chromatogram condition: chromatographic column: AgilentC18 (4.6 × 150mm, 5 μm); Flow velocity: 0.5mL/min; Column temperature: 30 DEG C; Sample size: 5 μ L; Mobile phase A: acetonitrile, Mobile phase B: 0.01mol/L ammonium acetate, gradient elution, condition of gradient elution is as shown in table 2:

Table 2 Ultra Performance Liquid Chromatography condition of gradient elution

Mass Spectrometry Conditions: ion gun: negative ion (ESI-) and type collection; Electron spray voltage :-4500V (ESI-), 5000V (ESI+); Ion source temperature: 550 DEG C; Assisted gas Gas1 pressure: 60psi; Detection mode: multiple-reaction monitoring mode monitoring, analyze the quota ion of thing to, qualitative ion pair, go a bunch voltage (DP) and collision energy (CE) to see the following form 3.

Table 3 quota ion of analyzing thing to, qualitative ion pair, remove a bunch voltage (DP) and collision energy (CE)

Embodiment 2

Take ethanolic solution as solvent, preparation standard working curve, with continuous 10 sample introductions of least concentration standard solution, calculates standard deviation, represents detection limit and quantitative limit respectively, the results are shown in Table 4 with the standard deviation of 3 times and 10 times:

Table 4 method standard curvilinear equation and quantitative detection limit

Embodiment 3

To same sample carry out 5 times in a few days and in the daytime collimation measure, in a few days repeatability the results are shown in Table 5, and repeatability the results are shown in Table 6 in the daytime:

The in a few days repeated result (mg/kg) of table 5 method

In the daytime the repeated result (mg/kg) of table 6 method

Embodiment 4

After adopting standard solution sample to be carried out to the mark-on of variable concentrations level, according to method pre-treatment step processing sample, finally calculate its recovery of standard addition according to recovery testu, experimental result is as following table 7:

Table 7 method recovery of standard addition

As known from Table 7, the recovery of standard addition of sample, between 95.56-100.19%, illustrates that the recovery of this method is higher.

Embodiment 5

Choose the paper wrapper sample of candy often edible in daily life, hamburger, bread, biscuit 4 kinds of food, carry out the mensuration of Acid Light Yellow G according to the condition of embodiment 1, measurement result is in table 8.

The Acid Light Yellow G testing result of table 8 example paper food packaging materials sample

Claims

1. the assay method of Acid Light Yellow G in a paper food packaging materials, it is characterized in that: with the extract prepared by a certain percentage, ultrasonic extraction paper food packaging materials sample, directly enter Ultra Performance Liquid Chromatography-quadrupole rod GC-MS after extract filtering membrane to measure, quantified by external standard method.

2. the assay method of Acid Light Yellow G in a kind of paper food packaging materials according to claim 1, is characterized in that: described extract is ethanol-0.1% acetic acid-aqueous solution, wherein ethanol: 0.1% acetic acid: water volume ratio is 1:3:6.

3. the assay method of Acid Light Yellow G in a kind of paper food packaging materials according to claim 1, it is characterized in that, described filter membrane is 0.22 μm of organic filter membrane.

4. the assay method of Acid Light Yellow G in a kind of paper food packaging materials according to claim 1, it is characterized in that, the chromatographic condition in described step is as follows:

Chromatographic column: AgilentC18 (4.6 × 150mm, 5 μm);

Flow velocity: 0.5mL/min;

Column temperature: 30 DEG C;

Sample size: 5 μ L;

Mobile phase A: acetonitrile, Mobile phase B: 0.01mol/L ammonium acetate;

Gradient elution program is as following table:

5. the assay method of Acid Light Yellow G in a kind of paper food packaging materials according to claim 1, it is characterized in that, the Mass Spectrometry Conditions in described step is as follows:

Electric spray ion source: negative ion (ESI-) type collection

Electron spray voltage :-4500V (ESI-), 5000V (ESI+);

Ion source temperature: 550 DEG C;

Assisted gas Gas1 pressure: 60psi;

Detection mode: multiple-reaction monitoring mode monitoring

The quota ion of each analysis thing to, qualitative ion pair, go a bunch voltage (DP) and collision energy (CE) to see the following form:

6. the assay method of Acid Light Yellow G in a kind of paper food packaging materials according to claim 1, it is characterized in that, the method comprises the following steps:

(1) preparation of extract: the ethanol of 1:3:6 preparation by volume-0.1% acetic acid-water extract is for subsequent use;

(2) standard working curve makes: be solvent with ethanol, Acid Light Yellow G standard reserving solution is made into the standard solution of different series concentration, carries out Ultra Performance Liquid Chromatography-quadrupole rod GC-MS and detect; Then carry out linear regression with the concentration (X) of ratio (Y) to measured object of the peak area of measured object and its outer target peak area, try to achieve the typical curve of Acid Light Yellow G;

(3) sample preparation and analysis: accurately take 1.0g paper food packaging materials sample to be measured, put into 50ml ground triangular flask, accurately add 30mL extraction solution, ultrasonic 15min, after extraction solution through 0.22 μm of organic membrane filtration laggard enter Ultra Performance Liquid Chromatography-quadrupole rod GC-MS analyze.