CN107490650A - The assay method of fat-soluble colouring agent in a kind of ultra performance liquid chromatography tandem mass spectrum detection cigarette paper - Google Patents
The assay method of fat-soluble colouring agent in a kind of ultra performance liquid chromatography tandem mass spectrum detection cigarette paper Download PDFInfo
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- CN107490650A CN107490650A CN201710849385.2A CN201710849385A CN107490650A CN 107490650 A CN107490650 A CN 107490650A CN 201710849385 A CN201710849385 A CN 201710849385A CN 107490650 A CN107490650 A CN 107490650A
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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
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
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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
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
- G01N2030/062—Preparation extracting sample from raw material
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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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- Cigarettes, Filters, And Manufacturing Of Filters (AREA)
Abstract
The invention belongs to the physical and chemical inspection technical field that harmful substance in cigarette paper remains, the assay method of fat-soluble colouring agent in specifically a kind of cigarette paper, it is characterised in that：Add acetone after cigarette is shredded with paper first, then ultrasonic extraction, after the purification of extract dispersive solid-phase extraction, centrifugation, filter directly with the fat-soluble colouring agent in ultra performance liquid chromatography tandem mass spectrum measure paper.This method can quickly, accurately detect fat-soluble residual colorant left amount in paper, have method environmental protection, result be accurate, interference less, high sensitivity and it is reproducible the advantages of.
Description
Technical field
The invention belongs in cigarette paper harmful substance remain physical and chemical inspection technical field, relate generally to tobacco lining paper,
The assay method of fat-soluble colouring agent in tipping paper, bar box packaging paper, cigarette paper, liposoluble is specifically extracted using ultrasonic power
Property colouring agent, dispersive solid-phase extraction purification after, with the direct method for measuring of ultra performance liquid chromatography-tandem mass spectrum.
Background technology
Artificial synthesized colouring agent mainly using the aromatic hydrocarbons such as benzene, toluene, naphthalene chemical products as raw material, by sulfonation, nitrification,
A series of organic reactions such as halogenation, azo are bound up, itself without nutritive value, but due to its cost it is cheap, it is bright in colour,
Strong coloring force, property are stable and color matching is convenient, and it is beautiful and improve the appetite of people to increase the sense organ of food, in food production plus
It is widely used in industrial and commercial bank's industry.Synthetic coloring matter in food contact material can be entered by modes such as skin contact, migrations
In human body, so as to damaged to health [Zhao Xuerong etc., Speciality Petrochemicals, 2012,29 (6):30].Fat-soluble coloring
Agent, all there is strong toxicity, mutagenicity, carcinogenicity and teratogenesis as tonyred 1, tonyred 2 etc..Research shows,
The artificial synthesized colouring agent of Excess free enthalpy, it will accumulate in vivo, and artificial synthesized edible coloring agent is mostly azo compound,
Azo-compound decomposes in vivo, can form mutagen precursor-aromatic amine compounds, kidney, liver is produced certain
Injury, it is very big to eater's health hazard.At present, to the measure of colouring agent mainly using high performance liquid chromatography [field is richly endowed etc.,
Chemical analysis measures, 2012,21 (6):36], gas chromatography-mass spectrography [Liu Li etc., analytical chemistry, 2004,32 (10):1333
].These method matrix interferences are big, and colorant assortment is more, it is difficult to are kept completely separate, liquid chromatography-tandem mass spectrometry uses react more
Such issues that ion monitoring mode can overcome.
The content of the invention：
A kind of ultra performance liquid chromatography that the purpose of the present invention is based on above-mentioned current condition and provided-tandem mass spectrum detection cigarette
With the assay method of fat-soluble colouring agent in paper, this method overcomes prior art defect, quickly, accurately can detect in paper
Fat-soluble residual colorant left amount, method environmental protection, and measurement result is accurate, interference is few.
The present invention is in view of above-mentioned existing analysis method, it is contemplated that and the content of fat-soluble colouring agent is very low in Cigarette paper,
And fat-soluble colouring agent boiling point is higher, the characteristics of big is disturbed therefore from high sensitivity, the ultra high efficiency liquid of strong antijamming capability
The method analysis of phase chromatogram-tandem mass spectrum.
The purpose of the present invention is achieved through the following technical solutions：
The assay method of fat-soluble colouring agent, first uses cigarette in a kind of ultra performance liquid chromatography-tandem mass spectrum detection cigarette paper
Paper shred after plus acetone, then ultrasonic extraction, extract be dispersed through Solid phase extraction, centrifugation after, filtering and through dilution in acetonitrile
Directly specifically include following steps in the method for fat-soluble colouring agent in ultra performance liquid chromatography-tandem mass spectrum measure paper afterwards：
A, 0.5 g samples are weighed（It is accurate to 0.01 g）, it is placed in 50 mL conical flask with stopper.
B, the extraction of sample：It is accurate to add 20 mL extracts：Acetone, the min of ultrasonic extraction 30；
C, sample purification：5 min are stood, pipette the mL of extract 1.5 in 2 mL centrifuge tubes（Include 25mg neutral aluminas）In,
After 2000 rpm speed vortex oscillations 2min, 5 min are centrifuged with 8000 rpm speed.1mL supernatants are drawn, nitrogen blows closely
It is dry, redissolved with 1mL acetonitriles, filtered through 0.22 μm of organic phase filter membrane.
D, 200 μ L filtrate is pipetted, sample is diluted to 1.0 mL with acetonitrile, enters LC-MS/MS points as sample prepare liquid
Analysis；
E, standard working solution is prepared：5 mg fat-soluble colouring agent standard items are weighed into 10mL volumetric flasks, use dilution in acetonitrile
And finally it is configured to the standard working solution with concentration gradient；
F, liquid chromatography tandom mass spectrometry determination:The standard working solution and sample prepare liquid of the various concentrations prepared are drawn,
It is injected separately into liquid chromatography-tandem mass spectrometry instrument；
G, the calculating of fat-soluble colouring agent measurement result
Quantitative analysis is carried out with external standard method, i.e., its respective concentration returned with the quota ion pair peak area of fat-soluble colouring agent
Return analysis, obtain standard curve, coefficient correlation is more than or equal to 0.99.Sample prepare liquid after extraction is measured, measures inspection
Go out the quota ion pair peak area of fat-soluble colouring agent, substitute into the residual that standard curve tries to achieve the fat-soluble colouring agent in sample
Amount.
The manner of formulation of standard working solution is as follows in the present invention：Accurately 5 mg fat-soluble colouring agent is weighed in 10
In mL volumetric flasks, 0.1 mg is accurate to, with acetone solution and constant volume, it is 500 μ g/mL Standard Stock solutions to be configured to concentration；Point
100 μ L Standard Stock solutions are not pipetted into 10 mL volumetric flasks, and with acetone constant volume, this concentration of standard solution is 5.0 μ g/mL；
The working solution of certain volume is pipetted respectively in 10 mL volumetric flasks, with dilution in acetonitrile constant volume, that is, is configured to the mark of various concentrations
Quasi- working solution, series standard working solution concentration are respectively：20 ng/mL, 50 ng/mL, 100 ng/mL, 200 ng/mL,
With 500 ng/mL.
The liquid phase chromatogram condition used for：Chromatographic column：The quick posts of Poroshell 120EC C18 (mm of 100 mm × 4.6,
2.7 μm)；Mobile phase A：Acetonitrile, Mobile phase B：The % aqueous formic acids of 20 mmol ammonium acetates -0.1（Wherein contain 0.1 % formic acid,
v/v）, flow velocity：500μL/min；Column temperature：40 ℃；Sample size：2μL；Eluent gradient elution program is shown in Table 2.The mass spectrum of use
Condition：Scan mode：Cation scans;Electric spray ion source (ESI);Ion source temperature：150 ℃；Desolvation temperature：
350 ℃；Desolventizing gas flow：800 L/h；Residence time：30 ms；Capillary voltage：2.4 kV；Detection mode：Polyion
Reaction monitoring（MRM）, MRM parameters are shown in Table 1.
The method of the present invention overcomes the deficiency of prior art sample treatment, for cigarette tipping paper, internal lining paper and cigarette
Bar optimizes sample-pretreating method and instrument testing conditions with box packaging paper, cigarette paper sample.This hair compared with prior art
Bright method has following excellent results：
（1）The inventive method determines the content of fat-soluble colouring agent in paper using UPLC-MS/MS, and anti-matrix interference ability is strong,
Pre-treating method is simple.
（2）The present invention carries out dispersive solid-phase extraction using neutral alumina, can be very good despumation interference, raising point
The sensitivity of analysis.
（3）The present invention reduces the interference of matrix effect by the method for dilution.Because sample is in extraction process, analysis
There are many extracts to be altogether present in extract solution while target is extracted, determine so as to influence target in analytical instrument
Property quantitative analysis is, it is necessary to consider influence of the matrix effect to detection.Matrix effect generally can not be eliminated, but pass through some effective
Its influence can be reduced.The present invention compared for solvent standard curve and each concentration point response signal of extraction standard curve.Matrix pair
The influence of response signal is fairly obvious.But with the increase of extension rate, influence of the matrix effect to response signal, which has, substantially to be changed
It is kind.For tipping paper, each concentration point response signal of extraction standard curve of 5 times of dilution can reach same concentration standard liquid response
80% or so of signal.Other Cigarette papers（Internal lining paper, bar box packaging paper, paperboard）There is similar result.Extension rate is got over
Height, the influence of matrix effect are smaller.But extension rate is too high, the concentration of target is also reducing in sample, so as to the side of influence
The quantitative limit and detection limit of method.Binding experiment result final choice sample extracting solution dilutes 5 times of sample detections.
（4）The inventive method have operation accurate, high sensitivity and it is reproducible the advantages of.
1. the test limit of the inventive method：
The standard working solution of various concentrations is injected into UPLC-MS/MS, with 3 times of signal to noise ratio（S/N = 3）Calculate test limit
（LOD）.
2. the repeatability and recovery of standard addition of the inventive method：
The standard liquid of fat-soluble colouring agent is added in blank sample, then carries out pre-treatment and UPLC-MS/MS points respectively
Analysis, and according to adding scalar sum measured value to calculate its recovery.
The range of linearity of fat-soluble colouring agent, the rate of recovery reach, and average relative standard's deviation, detection limit is shown in Table 3.
Brief description of the drawings
Fig. 1 is the assay method flow chart of the present invention（The figure is as Figure of abstract）.
Embodiment
The present invention is described further below in conjunction with example, but is not the limitation present invention.
Example 1：
1. instrument and reagent：
Fat-soluble colouring agent, acetonitrile, acetone are chromatographic grade reagent；Meet the requirement of one-level water in GB/T 6682.
Waters TQS quadrupole rod tandem mass spectrometers；The electronic balances of Switzerland Mettler AE 163（Sensibility reciprocal：0.0001g）.
2. sample treatment：
Weigh 0.5 g bar box packaging paper samples（It is accurate to 0.01 g）, it is placed in 50 mL conical flask with stopper.It is accurate to add 20
ML extracts：Acetone, the min of ultrasonic extraction 30；Sample purification：5 min are stood, the mL of extract 1.5 is pipetted and is centrifuged in 2 mL
Pipe（Include 25mg neutral aluminas）In, after 2000 rpm speed vortex oscillations 2min, 5 are centrifuged with 8000 rpm speed
min.1mL supernatants are drawn, nitrogen, which blows, closely to be done, and is redissolved with 1mL acetonitriles, is filtered through 0.22 μm of organic phase filter membrane.Pipette 200 μ L's
Filtrate, sample is diluted to 1.0 mL with acetonitrile, enters UPLC-MS/MS analyses as sample prepare liquid；
3. prepare standard working solution：The accurate fat-soluble colouring agent for weighing 5 mg is accurate to 0.1 in 10 mL volumetric flasks
Mg, with acetone solution and constant volume, it is 500 μ g/mL Standard Stock solutions to be configured to concentration；It is molten that 100 μ L standard inventories are pipetted respectively
Liquid is into 10 mL volumetric flasks, and with acetone constant volume, this concentration of standard solution is 5.0 μ g/mL；The work of certain volume is pipetted respectively
Solution is in 10 mL volumetric flasks, with dilution in acetonitrile constant volume, that is, is configured to the standard working solution of various concentrations, series standard work
It is respectively as solution concentration：20 ng/mL, 50 ng/mL, 100 ng/mL, 200 ng/mL, and 500 ng/mL；
4. assay method:Quantitative analysis is carried out with external standard method, i.e., with the quota ion pair peak area of fat-soluble colouring agent to its phase
Answer concentration to carry out regression analysis, obtain standard curve, coefficient correlation is all higher than being equal to 0.99, the sample after extraction is surveyed
It is fixed, the quota ion pair peak area of detection object is measured, the content that substitution standard curve tries to achieve citrus red2 number in sample is
0.10 mg/kg。
For the accuracy of determination methods, 0.10 mg citrus red2 standard liquid is added in this sample, is same as above
Sample pre-treatments, the selection ion peak areas of citrus red2 number is measured with UPLC-MS/MS, standard curve is substituted into, tries to achieve now
The content of citrus red2 number in sample is 0.18 mg/kg, i.e., the recovery of standard addition of citrus red2 number is 90%, illustrates the method
It is accurate.
Example 2：
Method as described in Example 1, another cigarette tipping paper sample is selected, fat-soluble colouring agent is not detected in sample.
Example 3：
Method as described in Example 1, another cigarette paper sample is selected, fat-soluble colouring agent is not detected in sample.
Claims (4)
1. the assay method of fat-soluble colouring agent, its feature exist in a kind of ultra performance liquid chromatography-tandem mass spectrum detection cigarette paper
In：After cigarette is shredded with paper first plus acetone, then ultrasonic extraction, after the purification of extract dispersive solid-phase extraction, centrifugation, filtering,
And specifically included after dilution in acetonitrile directly with the fat-soluble colouring agent in ultra performance liquid chromatography-tandem mass spectrum measure paper
Following steps：
A, 0.5 g samples are weighed, are placed in 50 mL conical flask with stopper；
B, the extraction of sample：It is accurate to add 20 mL extracts：Acetone, the min of ultrasonic extraction 30；
C, sample purification：5 min are stood, pipette the mL of extract 1.5 in the 2 mL centrifuge tube for including 25mg neutral aluminas
In, with 2000 rpm speed vortex oscillation 2min, 5 min are centrifuged with 8000 rpm speed, draw 1mL supernatants, nitrogen blows closely
It is dry, redissolved with 1mL acetonitriles, filtered through 0.22 μm of organic phase filter membrane；
D, 200 μ L filtrate is pipetted, sample is diluted to 1.0 mL with acetonitrile, enters UPLC-MS/MS points as sample prepare liquid
Analysis；
E, standard working solution is prepared：5 mg fat-soluble colouring agent standard items are weighed into 10mL volumetric flasks, use dilution in acetonitrile
And finally it is configured to the standard working solution with concentration gradient；
F, liquid chromatography tandom mass spectrometry determination:The standard working solution and sample prepare liquid of the various concentrations prepared are drawn,
It is injected separately into liquid chromatography-tandem mass spectrometry instrument；
The liquid phase chromatogram condition used for：Chromatographic column：The quick posts of Poroshell 120EC C18, the mm of the mm of specification 100 × 4.6,
2.7 μm；Mobile phase A：Acetonitrile, B：The % aqueous formic acids of 20 mmol ammonium acetates -0.1, flow velocity：500 μ L/min, gradient elution；
Column temperature：40 ℃；Sample size：2μL；
The Mass Spectrometry Conditions of use：Scan mode：Cation scans;Electric spray ion source (ESI);Ion source temperature：150 ℃；
Desolvation temperature：350 ℃；Desolventizing gas flow：800 L/h；Residence time：30 ms；Capillary voltage：2.4 kV；Inspection
Survey mode：Polyion reaction monitoring（MRM）；
G, the calculating of fat-soluble colouring agent measurement result
Quantitative analysis is carried out with external standard method, i.e., its respective concentration returned with the quota ion pair peak area of fat-soluble colouring agent
Return analysis, obtain standard curve, coefficient correlation is more than or equal to 0.999；Sample prepare liquid after extraction is measured, measures inspection
Go out the quota ion pair peak area of fat-soluble colouring agent, substitute into the residual that standard curve tries to achieve the fat-soluble colouring agent in sample
Amount.
2. assay method according to claim 1, it is characterised in that：The manner of formulation of standard working solution is as follows：Accurately
5 mg fat-soluble colouring agent is weighed in 10 mL volumetric flasks, is accurate to 0.1 mg, with acetone solution and constant volume, is configured to dense
Spend for 500 μ g/mL Standard Stock solutions；100 μ L Standard Stock solutions are pipetted respectively into 10 mL volumetric flasks, are determined with acetone
Hold, this concentration of standard solution is 5.0 μ g/mL；The working solution of certain volume is pipetted respectively in 10 mL volumetric flasks, uses acetonitrile
Constant volume is diluted, that is, is configured to the standard working solution of various concentrations, series standard working solution concentration is respectively：20 ng/mL,
50 ng/mL, 100 ng/mL, 200 ng/mL, and 500 ng/mL.
3. assay method according to claim 1, it is characterised in that：In step f, the gradient elution program such as following table
。
4. assay method according to claim 1, it is characterised in that：The cigarette with paper be tobacco lining paper, tipping paper or
Bar box packaging paper, cigarette paper.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108303481A (en) * | 2018-01-31 | 2018-07-20 | 山东省食品药品检验研究院 | The universal test method of citrus red2 number and Sudan red dyes in food |
| CN109254095A (en) * | 2018-10-22 | 2019-01-22 | 河北农业大学 | It is a kind of for detecting the ultra performance liquid chromatography tandem mass spectrum detection method of gossypol content in agricultural and sideline product |
-
2017
- 2017-09-20 CN CN201710849385.2A patent/CN107490650A/en active Pending
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108303481A (en) * | 2018-01-31 | 2018-07-20 | 山东省食品药品检验研究院 | The universal test method of citrus red2 number and Sudan red dyes in food |
| CN109254095A (en) * | 2018-10-22 | 2019-01-22 | 河北农业大学 | It is a kind of for detecting the ultra performance liquid chromatography tandem mass spectrum detection method of gossypol content in agricultural and sideline product |
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Application publication date: 20171219 |