CN102095814B - Method for determining volatile nitrosamines in cosmetics - Google Patents
Method for determining volatile nitrosamines in cosmetics Download PDFInfo
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- CN102095814B CN102095814B CN201010576976A CN201010576976A CN102095814B CN 102095814 B CN102095814 B CN 102095814B CN 201010576976 A CN201010576976 A CN 201010576976A CN 201010576976 A CN201010576976 A CN 201010576976A CN 102095814 B CN102095814 B CN 102095814B
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Abstract
The invention relates to a method for determining volatile nitrosamines in cosmetics by gas chromatography-mass spectrometry or mass spectrometry. The method is accurate and reliable, and the detection limit, the recovery rate and the precision meet the requirement. The invention establishes a method capable of simultaneously determining 10 types of volatile nitrosamines in the cosmetics by gas chromatography-tandem quadrupole mass spectrometry. The method is accuracy, quick and has high sensitivity, and can provide the scientific basis and the technical supports for the nitrosamine contamination monitoring and the product quality control of the cosmetics.
Description
Technical field
The present invention relates to the assay method of volatile nitrosamine in a kind of cosmetics.
Background technology
Nitrosamine compound is one type of organic compound (seeing table 1) with similar structures, and animal is had carcinogenesis, in more than 300 kind of nitrosamine compound of people's research, has more than 90% the examination animal is had carcinogenicity.Nitrosamine in the cosmetics possibly formed through nitrosation reaction by nitrogen-containing compounds such as the secondary amine in the raw material, tertiary amine, quaternary amine, acid amides, alkyl amine, amine oxides in Cosmetic Manufacture and put procedure from raw material on the one hand on the other hand.Nitrosamine in the cosmetics can absorb through skin and get into human body, discovers, after the skin contact contains the cosmetics of N-nitrosodiethanolamine, in urine, can detect this composition, therefore can constitute great potential hazard to health.In China's cosmetics health standard and the European Union's cosmetics rules (Council Directive 76/768/EEC) all clearly in the regulation cosmetics nitrosamine compound be banned substance in the components of cosmetics.In the cosmetics handbook (CosmeticHandbook) of U.S. FDA promulgation clearly the regulation nitrosamine compound be banned substance in the components of cosmetics.
Table 110 kind of volatile nitrosamine standard items
The detection of nitrosamine research mainly concentrates on the N-nitrosodiethanolamine in the cosmetics; The method that adopts comprises that assay method, gas chromatography-mass spectrography, capillary electric chromatogram method, polarography, the liquid chromatography of gas chromatography configuration heat energy or electron capture detector dispose the assay method of heat energy, ultraviolet or fluorescence detector, LC/MS etc., and the domestic and international at present mensuration about volatile nitrosamines such as N-nitroso-dimethyl amines in the cosmetics then rarely has report.
Summary of the invention
The technical matters that the present invention solved provides a kind of accurate, quick, highly sensitive, the detection method of volatile nitrosamine in the cosmetics that can scientific basis and technical support be provided for the monitoring and the production quality control of nitrosamine pollution situation in the cosmetics.
For achieving the above object, the technical scheme that the present invention adopts is following: the assay method of volatile nitrosamine in a kind of cosmetics may further comprise the steps:
(1) sample is handled: take by weighing the 1.0g sample in 50mL tool plug conical flask, add the 10mL organic solvent, ultrasonic Extraction 15-30min is to be not less than the centrifugal 15min of 5000r/min; Pipette the 2mL supernatant, nitrogen slowly dries up; Do liquid to be clean after adding the dissolving of 2mL 30% methanol aqueous solution; Liquid to be clean is transferred in the solid-phase extraction column, with 3mL30% methanol aqueous solution washing, be evacuated near doing after, use the 8mL methanol-eluted fractions; Eluent dries up with nitrogen under 50 ℃, and residue is used the 1mL methanol constant volume, and vortex mixed 1min behind the miillpore filter, supplies GC-MS/MS to measure excessively;
(2) measure: adopt gas chromatography-mass spectrum/mass spectrometry method, wherein chromatogram column temperature rises to 260 ℃ with the programming rate of 30 ℃/min; Injector temperature: 250 ℃; Chromatography-mass spectroscopy interface temperature: 250 ℃; Ion source temperature: 180 ℃; Carrier gas: helium, purity >=99.999%; Flow velocity: 1.0mL/min; Sample size: 1 μ L;
(3) drawing standard working curve: accurately draw standard operation solution respectively and be mixed with the standard solution that concentration is 50 μ g/L, 100 μ g/L, 250 μ g/L, 500 μ g/L, 1mg/L, 5mg/L, 10mg/L; Drawing respectively accurately 1 μ L injection gas chromatography-series connection quadrupole mass spectrometer, according to detecting under the above-mentioned analysis condition, is ordinate with the peak area of quota ion, and the concentration corresponding with it is horizontal ordinate, the drawing standard working curve.
The inventive method adopts the volatile nitrosamine in gas chromatography-mass spectrum/mass spectrometric determination cosmetic, and method is accurate, reliable, and detectability, the recovery and precision all meet the requirements.The present invention has set up gas chromatography-series connection quadrupole rod mass spectrometric analysis method of measuring 10 kinds of volatile nitrosamines in the cosmetics simultaneously; Method is accurate, quick, highly sensitive, can scientific basis and technical support be provided for the monitoring and the production quality control of nitrosamine pollution situation in the cosmetics.
Embodiment
For further specifying the present invention, specify in conjunction with following examples:
1, reagent and material:
Except as otherwise noted, it is pure that agents useful for same is analysis, and water is the one-level water of GB/T 6682 regulations.
1.1 methyl alcohol.
1.2 methylene chloride.
1.3 acetone.
1.4 absolute ethyl alcohol.
1.5N-nitroso-dimethyl amine (N-Nitrosodimethylamine) standard substance: purity is more than or equal to 97%.
1.6N-nitroso-diethylamide (N-Nitrosodiethylamine) standard substance: purity is more than or equal to 98%.
1.7N-nitroso-dipropylamine (N-Nitrosodi-n-propylamine) standard substance: purity is more than or equal to 99%.
1.8N-nitrosomorpholine (N-Nitrosomorpholine) standard substance: purity is more than or equal to 99%.
1.9N-nitrosopyrolidine (N-Nitrosopyrrolidine) standard substance: purity is more than or equal to 97%.
1.10N-nitroso-piperidine (N-Nitrosopiperidine) standard substance: purity is more than or equal to 98%.
1.11N-nitroso-dibutylamine (N-Nitrosodi-n-butylamine) standard substance: purity is more than or equal to 97%.
1.12N-nitroso-diphenylamine (N-Nitrosodiphenylamine) standard substance: purity is more than or equal to 97%.
1.13N-nitroso-dicyclohexyl amine (N-Nitrosodicyclohexylamine) standard substance: purity is more than or equal to 99%.
1.14N-nitroso-dibenzyl amine (N-Nitrosodibenzylamine) standard substance: purity is more than or equal to 99%.
1.15 volatile nitrosamine standard reserving solution: accurately take by weighing each volatile nitrosamine standard items of 10mg (being accurate to 0.0001g) respectively, place the 100mL volumetric flask, be diluted to scale with methyl alcohol, mixing, the concentration of this solution is 100mg/L.
1.16 the preparation of mixed standard solution: pipette an amount of volume of each standard reserving solution respectively,, be mixed with the mixed standard solution that concentration is 10mg/L with the methyl alcohol dilution.
1.17 solid-phase extraction column: matrix is N-vinylpyrrolidone-divinyl aniline, 200mg, 6mL, or suitable person.Use 6mL methyl alcohol, the activation of 6mL water before the use successively.
2, instrument and equipment
2.1 gas chromatography-series connection quadrupole mass spectrometer (GC-MS/MS): be furnished with electron impact ionization source (EI).
2.2 analytical balance: sensibility reciprocal is 0.0001g and 0.001g.
2.3 hydro-extractor: rotating speed is not less than 5000r/min.
2.4 ultrasound bath.
2.5 solid-phase extraction device.
2.6 nitrogen dries up appearance.
2.7 turbine mixer.
2.8 filter membrane: 0.45 μ m, organic phase.
3, determination step
3.1 sample is handled
3.1.1 extract
3.1.1.1 cream kind sample
Take by weighing 1.0g (being accurate to 0.001g) sample in 50mL tool plug conical flask, add 10mL methyl alcohol-methylene chloride mixed liquor (8: 2, volume fraction), ultrasonic Extraction 30min is to be not less than the centrifugal 15min of 5000r/min.Pipette the 2mL supernatant, nitrogen slowly dries up.Do liquid to be clean after adding the dissolving of 2mL 30% methanol aqueous solution.
3.1.1.2 aqua class sample
Take by weighing 1.0g (being accurate to 0.001g) sample in 50mL tool plug conical flask, add 10mL acetone, ultrasonic Extraction 15min is to be not less than the centrifugal 15min of 5000r/min.Pipette the 2mL supernatant, nitrogen slowly dries up.Do liquid to be clean after adding the dissolving of 2mL 30% methanol aqueous solution.
3.1.1.3 shampoo class sample
Take by weighing 1.0g (being accurate to 0.001g) sample in 50mL tool plug conical flask, add 10mL methyl alcohol-acetone mixed liquor (5: 5, volume fraction), ultrasonic Extraction 30min is to be not less than the centrifugal 15min of 5000r/min.Pipette the 2mL supernatant, nitrogen slowly dries up.Do liquid to be clean after adding the dissolving of 2mL 30% methanol aqueous solution.
3.1.1.4 lipstick class cosmetics
Take by weighing 1.0g (being accurate to 0.001g) sample in 50mL tool plug conical flask, add 10mL absolute ethyl alcohol-acetone mixed liquor (8: 2, volume fraction), ultrasonic Extraction 30min is to be not less than the centrifugal 15min of 5000r/min.Pipette the 2mL supernatant, nitrogen slowly dries up.Do liquid to be clean after adding the dissolving of 2mL 30% methanol aqueous solution.
3.1.1.5 loose powder class cosmetics
Take by weighing 1.0g (being accurate to 0.001g) sample in 50mL tool plug conical flask, add 10mL methyl alcohol, ultrasonic Extraction 30min is to be not less than the centrifugal 15min of 5000r/min.Pipette the 2mL supernatant, nitrogen slowly dries up.Do liquid to be clean after adding the dissolving of 2mL 30% methanol aqueous solution.
3.1.2 purify
Liquid to be clean among the 3.1.1 is transferred in the solid-phase extraction column.With 3mL 30% methanol aqueous solution washing, be evacuated near doing after, use the 8mL methanol-eluted fractions.Whole SPE process flow velocity is no more than 1mL/min.Eluent dries up with nitrogen under 50 ℃, and residue is used the 1mL methanol constant volume, and vortex mixed 1min behind the miillpore filter (5.8), supplies GC-MS/MS to measure excessively.
3.2 measure
3.2.1 gas chromatography-mass spectrum/mass spectrum condition
Because test result depends on employed instrument, therefore can not provide the general parameter of stratographic analysis.It is suitable adopting the following operations condition to be proved to be test.
A) chromatographic column: DB-624 quartz capillary column, 30m * 0.25mm (i.d.) * 0.25 μ m, or suitable person;
B) chromatogram column temperature:
C) injector temperature: 250 ℃;
D) chromatography-mass spectroscopy interface temperature: 250 ℃;
E) ion source temperature: 180 ℃;
F) carrier gas: helium, purity >=99.999%; Flow velocity: 1.0mL/min;
G) sample size: 1 μ L;
H) input mode: split sampling not, drive valve behind the 0.5min;
I) ionization mode: EI;
J) mass scanning scope: (50～1000) amu;
K) ionizing energy: 70eV;
1) trap electric current: 200 μ A;
M) solvent delay: 3min;
N) monitoring mode: MRM;
O) Multiplier voltage: 500V.
3.2.2 the drafting of standard working curve
Accurately draw standard operation solution respectively and be mixed with the standard solution that concentration is 50 μ g/L, 100 μ g/L, 250 μ g/L, 500 μ g/L, 1mg/L, 5mg/L, 10mg/L.Drawing respectively accurately 1 μ L injection gas chromatography-series connection quadrupole mass spectrometer, according to experimentizing under the above-mentioned analysis condition, is ordinate with the peak area of quota ion, and the concentration corresponding with it is horizontal ordinate, the drawing standard working curve.Can draw as required and be no less than 4 typical curve.
3.3 blank test
Except that not adding the sample, all undertaken by above-mentioned steps.
4, the result calculates
The result calculates by formula (1), and result of calculation keeps two-decimal:
In the formula:
W---the massfraction of nitrosamine in the cosmetics, unit is every kilogram (mg/kg) of milligram;
C---the concentration of nitrosamine from the sample solution that standard working curve is found, unit is every liter (mg/L) of milligram;
V---sample constant volume, unit is for rising (L);
The quality of m---sample, unit is gram (g).
5, the linear relationship of method and detection limit
5.1 linear relationship
Under the determined experiment condition of this method of inspection; Get series of standards solution 50 μ g/L, 100 μ g/L, 250 μ g/L, 500 μ g/L, 1mg/L, 5mg/L, 10mg/L; Peak area (Y axle) with nitrosamine is mapped to corresponding concentration (X axle), and the linear equation and the regression coefficient of each nitrosamine are seen table 2.When the nitrosamine concentration in the sample surpasses this range of linearity, can suitably strengthen the dilution of sample multiple.
The linear equation of table 210 kind of volatile nitrosamine, regression coefficient and mensuration lower bound
| Chinese | Linear equation | Regression coefficient r | Measure lower bound (mg/kg) |
| N-nitroso-dimethyl amine | Y＝5.6363X+0.3247 | 0.9969 | 10.0 |
| N-nitroso-diethylamide | Y＝60.3079X-11.9077 | 0.9960 | 2.5 |
| N-nitroso-dipropylamine | Y＝60.2106X-13.9230 | 0.9955 | 2.5 |
| N-nitrosomorpholine | Y＝9.8695X-1.9940 | 0.9954 | 2.5 |
| The N-nitrosopyrolidine | Y＝16.8586X-3.2914 | 0.9960 | 5.0 |
| N-nitroso-piperidine | Y＝54.4912X-12.9403 | 0.9955 | 2.5 |
| N-nitroso-dibutylamine | Y＝34.2132X-6.7912 | 0.9966 | 2.5 |
| N-nitroso-diphenylamine | Y＝110.1460X-12.3830 | 0.9986 | 2.5 |
| N-nitroso-dicyclohexyl amine | Y＝1.5419X+0.0284 | 0.9978 | 10.0 |
| N-nitroso-dibenzyl amine | Y＝2050X-79.4030 | 0.9984 | 2.5 |
5.2 the detection limit of method
Through the laboratory experiment to the method for inspection, the mensuration lower bound of method is seen table 2.
6, the recovery of method and precision
The experiment of this standard method recovery has been set three and has been added concentration by the interpolation situation in the common cosmetics, by the determined experiment condition of this method of inspection, each is added concentration carry out 6 experiments, and the nitrosamine recovery is 85.2%～102.3%; Precision experiment (n=6) records relative standard deviation 3.05%～9.24%.The result is summarized in table 3.
7, conclusion
Comprehensive above-mentioned situation, the recovery of this standard test method, each item technical indicators such as detectability and precision all meet the requirements, and method is applied to cosmetic sample and detects, and reappearance is good.The method of inspection that this standard is set up is easy and simple to handle, the result is accurate, can be used for the check of volatile nitrosamine in the cosmetics.
Emphasis of the present invention is optimized above-mentioned experiment condition:
1, the optimization of chromatogram and mass spectrum condition
Investigated the gas chromatographic column of different fixing liquid, opposed polarity respectively: non-polar column (DB-5MS; 5% phenyl-95% methyl polysiloxane immobile liquid), middle polarity post (DB-624; 6% cyanogen propyl group phenyl-94% dimethyl polysiloxane immobile liquid), strong polar column (HP-INNOWax, polyglycol immobile liquid) is to the chromatographic resolution effect of 10 kinds of volatile nitrosamines.The result shows, selects for use the nonpolar capillary gas chromatographic column of DB-5MS to obtain best chromatographic peak profile and separating effect, in 15min, has accomplished the separation detection of 10 kinds of volatile nitrosamines.Investigated the ionization effect of nitrosamine under electron bombardment ionization source (EI) and chemical ionization source (CI) respectively, the result shows that 10 kinds of volatile nitrosamines can obtain the molecular ion peak than high abundance under EI ionization mode.Must reach 4 requirements of proving conclusively point according to the 2002/657/EC of European Union instruction regulation for the low liquid chromatography-mass spectrography conclusive evidence method of differentiating; Adopt the daughter ion scan mode to carry out the second order ms analysis; Daughter ion has been carried out optimized choice; Confirm quota ion and auxiliary qualitative ion, mass spectrum parameters such as scioptics voltage, collision energy, mass resolution make the molion of nitrosamine compound and the ion pair intensity of characteristic fragmention generation reach maximum.
2, the optimization of sample pre-treatments condition
Cosmetic sample method for distilling commonly used is vibration extraction, heating and extracting, Microwave Extraction, ultrasonic Extraction etc.In order to reduce operation steps and to obtain high as far as possible extraction efficiency, adopt the ultrasonic Extraction mode that sample is extracted.N-octyl alcohol/the water partition coefficient of 10 kinds of volatile nitrosamines (Kow) between-0.57 and 3.90, polarity scope wider distribution.To cream kind, aqua class, shampoo class, lipstick class, the dissimilar cosmetics sample of loose powder class, investigated different extraction solvents respectively, confirmed best sample extraction condition.Investigated the clean-up effect of dissimilar solid-phase extraction columns respectively: hydrophilic lipophilic post (Oasis HLB), silicagel column (Sep-Pak Silica), nh 2 column (Sep-Pak NH2), alumina column (Sep-Pak Alumina N) and florisil silica post (Sep-Pak Florisil) to nitrosamine compound.The result shows that the clean-up effect of Oasis HLB post and the recovery are optimum.Adopting Oasis HLB post is solid-phase extraction column, earlier with 6mL methyl alcohol activation stationary phase, and removes the impurity in the stationary phase, uses the 6mL water balance again, creates the environment that is fit to go up appearance.Investigate the elute effect of the methanol aqueous solution elution circuit of different proportionings, confirmed washing and elution requirement.
Above-described embodiment describes preferred implementation of the present invention; Be not that scope of the present invention is limited; Design under the prerequisite of spirit not breaking away from the present invention; Various distortion and improvement that the common engineering technical personnel in this area make technical scheme of the present invention all should fall in the definite protection domain of claims of the present invention.
Claims (1)
1. the assay method of volatile nitrosamine in the cosmetics is characterized in that: may further comprise the steps:
(1) sample is handled: take by weighing the 1.0g sample in 50mL tool plug conical flask, add the 10mL organic solvent, ultrasonic Extraction 15-30min is to be not less than the centrifugal 15min of 5000r/min; Pipette the 2mL supernatant, nitrogen slowly dries up; Do liquid to be clean after adding the dissolving of 2mL30% methanol aqueous solution; Liquid to be clean is transferred in the solid-phase extraction column, with 3mL 30% methanol aqueous solution washing, be evacuated near doing after, use the 8mL methanol-eluted fractions; Eluent dries up with nitrogen under 50 ℃, and residue is used the 1mL methanol constant volume, and vortex mixed 1min behind the miillpore filter, supplies GC-MS/MS to measure excessively;
(2) measure: adopt gas chromatography-mass spectrum/mass spectrometry method, wherein chromatographic column is the DB-624 quartz capillary column of 30m * 0.25mm * 0.25 μ m, and chromatogram column temperature rises to 260 ℃ with the programming rate of 30 ℃/min; Injector temperature: 250 ℃; Chromatography-mass spectroscopy interface temperature: 250 ℃; Ion source temperature: 180 ℃; Carrier gas: helium, purity >=99.999%; Flow velocity: 1.0mL/min; Sample size: 1 μ L;
(3) drawing standard working curve: accurately draw standard operation solution respectively and be mixed with the standard solution that concentration is 50 μ g/L, 100 μ g/L, 250 μ g/L, 500 μ g/L, 1mg/L, 5mg/L, 10mg/L; Drawing respectively accurately 1 μ L injection gas chromatography-series connection quadrupole mass spectrometer, detect according to the assay method of step (2), is ordinate with the peak area of quota ion, and the concentration corresponding with it is horizontal ordinate, the drawing standard working curve.
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| CN105353068B (en) * | 2015-12-09 | 2017-02-01 | 中国烟草总公司郑州烟草研究院 | GC-MS/MS assay determination method for volatile N-nitrosamine in tobacco and smokeless tobacco products |
| CN106501410A (en) * | 2016-10-27 | 2017-03-15 | 安徽易康达光电科技有限公司 | The detection method of N nitrosodiethanolamines in a kind of cosmetics |
| CN106770740A (en) * | 2016-12-05 | 2017-05-31 | 江西宜信堂医疗科技有限公司 | The detection method of N nitrosodimethylamines in a kind of malt or beer |
| CN108008040A (en) * | 2017-12-01 | 2018-05-08 | 暨南大学 | A kind of detection method of underwater trace N- nitrosamine |
| CN112710763B (en) * | 2021-01-06 | 2023-07-28 | 湖南威特制药股份有限公司 | Method for detecting N-nitrosodimethylamine in nizatidine by HPLC method |
| CN114924013A (en) * | 2022-05-12 | 2022-08-19 | 广东铭康香精香料有限公司 | Method for determining various perfume ingredients in cosmetics by gas chromatography-tandem mass spectrometry |
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