CN102062766B - Method for measuring nonyl phenol in cosmetic - Google Patents
Method for measuring nonyl phenol in cosmetic Download PDFInfo
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- CN102062766B CN102062766B CN201010576977.XA CN201010576977A CN102062766B CN 102062766 B CN102062766 B CN 102062766B CN 201010576977 A CN201010576977 A CN 201010576977A CN 102062766 B CN102062766 B CN 102062766B
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Abstract
The invention relates to a method for measuring nonyl phenol in cosmetic by liquid chromatography-mass spectrography/mass spectrography. The method is simple, convenient, quick, accurate and reliable, and detection limit, recovery rate and precision meet the requirements. The method is applied to the detection of a cosmetic sample, has high repeatability, and can be used for inspecting the nonyl phenol in the cosmetic.
Description
Technical field
The present invention relates to a kind of assay method of nonyl phenol in cosmetic.
Background technology
Nonyl phenol:
English name: Nonylphenol
CAS：84852-15-3
Molecular formula: C
15h
24o
Molecular weight: 220.35
Structural formula:
The potpourri that nonyl phenol is multiple isomeride, colourless to faint yellow thick liquid, slightly phenol smell.Density 0.94～0.95g/cm
3.(95%) 283～302 ℃ of boiling point.Water insoluble.Slightly be dissolved in sherwood oil.Be dissolved in acetone, phenixin, ethanol and chloroform.Mainly for the production of surfactant, also for fields such as antioxidant, textile auxiliary, oil dope, farm chemical emulgent, modifier, resin and rubber stabilizers.
Nonyl phenol is as typical phenols environmental estrogens, and its potential risk to environment and human health has caused people's extensive concern.Nonyl phenol is widely used as textile finshing agent, plastic plasticizer, industry and house detergent, agricultural chemicals and printing and dyeing emulsifying agent etc., and in a large number for the synthesis of the non-ionics NPE.Nonyl phenol, as endocrine disruptor, can accumulate in vivo, and enter human body by food chain, to human cancer cell's growth and fecundity, all can produce and have a strong impact on, and by European Union, is classified as preferential hazardous substance.Olso-Paris Convention (OSPAR) has also been listed nonyl phenol in priority pollutants matter register.
Summary of the invention
Technical matters solved by the invention be to provide a kind of accurately, reliable, detectability, the recovery and precision is the method for the micro-nonyl phenol in higher cosmeticses of everyday use such as Fast Measurement cosmetics all, is beneficial to the quality monitoring of Related product.
For achieving the above object, the technical solution used in the present invention is as follows:
A kind of assay method of nonyl phenol in cosmetic comprises the following steps:
(1) sample pretreating: take the about 0.5g of cosmetics sample, be placed in 50mL tool plug conical flask, add mark storing solution in 50 μ L, add again 10mL methyl alcohol or absolute ethyl alcohol and methylene chloride mixed solution, ultrasonic extraction 30min in ultrasonic cleaner, extract is moved in centrifuge tube, at the centrifugal 15min of 5000r/min speed, get supernatant 2mL after centrifugal, nitrogen slowly blows near dry, dissolve with 30% methanol aqueous solution vortex again, adopt 6mL methylene chloride and the activation of 6mL methyl alcohol, the isorrheic HLB Solid-Phase Extraction of 6mL column purification through in advance; The 2mL sample solution, with 1mL/min flow velocity loading, is used 3mL 30% methanol aqueous solution to clean, and 6mL methanol dichloromethane mixed solution is wash-out at twice; The gained eluent slowly blows near dry with nitrogen, uses the 2mL methanol constant volume, for liquid chromatography-tandem mass spectrometry, measures;
(2) measure: adopt liquid chromatography-mass spectrography/mass spectrometry method, wherein liquid phase chromatogram condition is: flow velocity: 0.25mL/min; Column temperature: 30 ℃; Sample size: 5 μ L; The mass spectrum condition is: capillary voltage: 1.5kV; Extraction voltage: 3V; Radio-frequency lens voltage: 0.5V; Ion source temperature: 150 ℃; Desolventizing temperature degree: 450 ℃;
(3) drawing standard working curve: accurately draw respectively the standard solution that the standard operation solution preparation becomes concentration to be 10 μ g/L, 50 μ g/L, 100 μ g/L, 250 μ g/L, 500 μ g/L, inner mark solution concentration is 50 μ g/L; Draw respectively accurately 5 μ L and inject liquid chromatography-series connection quadrupole mass spectrometers, according to being tested under above-mentioned analysis condition, the ratio of peak area of quota ion of take is ordinate, and the concentration corresponding with it is horizontal ordinate, the drawing standard working curve.
Method of the present invention, methyl alcohol or absolute ethyl alcohol described in wherein said step (1) are preferably with the mixed volume ratio of methylene chloride mixed solution: methyl alcohol or absolute ethyl alcohol: methylene chloride=8: 2.
Method of the present invention, in wherein said step (2), liquid chromatography preferably adopts methyl alcohol-0.1% ammonia spirit as mobile phase.
The inventive method adopts the nonyl phenol in liquid chromatography-mass spectrography/mass spectrometric determination cosmetics, and method is easy, quick, accurate, reliable, and detectability, the recovery and precision all meet the requirements.Method is applied to cosmetic sample and detects, and reappearance is good.Can, for the check of nonyl phenol in cosmetic.
Embodiment
For further illustrating the present invention, illustrate with the following Examples:
1, reagent and material
Except as otherwise noted, it is pure that agents useful for same is analysis, and water is secondary deionized water or double distilled water.
1.1 methyl alcohol: LC-MS level.
1.2 the nonyl phenol standard substance: purity is more than or equal to 98%.
1.34-n-the nonyl phenol standard substance: purity is more than or equal to 98%.
1.4 nonyl phenol standard inventory solution: accurately take appropriate nonyl phenol standard substance (being accurate to 0.1mg), the methyl alcohol of take is mixed with concentration as putting the standard inventory solution of 100mg/L.
1.54-n-mark stock solution in nonyl phenol: accurately take appropriate 4-n-nonyl phenol standard substance (being accurate to 0.1mg), the interior mark stock solution that it is 10mg/L that the methyl alcohol of take is mixed with concentration.
2, instrument and equipment
2.1 liquid chromatography-series connection quadrupole mass spectrometer: be furnished with electric spray ion source.
2.2 ultrasound bath.
2.3 analytical balance: sensibility reciprocal is 0.001g and 0.001g.
2.4 hydro-extractor: be greater than 5000r/min.
2.50.45 μ m organic system filtering membrane.
2.6 solid-phase extraction column (200mg, 6mL).
3, determination step
3.1 sample pretreating
3.1.1 cream kind, loose powder, aqua class sample
Take the about 0.5g of cosmetics sample (being accurate to 0.001g), be placed in 50mL tool plug conical flask, add mark storing solution in 50 μ L, add again 10mL methyl alcohol and methylene chloride mixed solution (8: 2, V/V), ultrasonic extraction 30min in ultrasonic cleaner, extract is moved in centrifuge tube, at the centrifugal 15min of 5000r/min speed, get supernatant 2mL after centrifugal, nitrogen slowly blows near dry, then dissolves with 30% methanol aqueous solution vortex, adopt 6mL methylene chloride and the activation of 6mL methyl alcohol, the isorrheic HLB Solid-Phase Extraction of 6mL column purification through in advance.The 2mL sample solution is with 1mL/min flow velocity loading, uses 3mL 30% methanol aqueous solution to clean, and 6mL methanol dichloromethane mixed solution (8: 2, V/V) wash-out at twice.The gained eluent slowly blows near dry with nitrogen, uses the 2mL methanol constant volume, for liquid chromatography-tandem mass spectrometry, measures.
3.1.2 lipstick class sample
Take the about 0.5g of cosmetics sample (being accurate to 0.001g), be placed in 50mL tool plug conical flask, add mark storing solution in 50 μ L, add again 10mL absolute ethyl alcohol and methylene chloride mixed solution (8: 2, V/V), ultrasonic extraction 30min in ultrasonic cleaner, extract is moved in centrifuge tube, at the centrifugal 15min of 5000r/min speed, get supernatant 2mL after centrifugal, nitrogen slowly blows near dry, then dissolves with 30% methanol aqueous solution vortex, adopt 6mL methylene chloride and the activation of 6mL methyl alcohol, the isorrheic HLB Solid-Phase Extraction of 6mL column purification through in advance.The 2mL sample solution is with 1mL/min flow velocity loading, uses 3mL 30% methanol aqueous solution to clean, and 6mL methanol dichloromethane mixed solution (8: 2, V/V) wash-out at twice.The gained eluent slowly blows near dry with nitrogen, uses the 2mL methanol constant volume, for liquid chromatography-tandem mass spectrometry, measures.
3.2 measure
3.2.1 liquid chromatography-mass spectrography/mass spectrum condition
Because test result depends on used instrument, therefore can not provide the general parameter of stratographic analysis.It is suitable adopting following operating conditions to be proved to be test.
(1) liquid phase chromatogram condition
A) chromatographic column: XBridge C
18post, 150mm * 2.1mm (internal diameter), 3.5 μ m (particle diameter), or suitable person.
B) mobile phase: methyl alcohol (A) and 0.1% ammonia spirit (B), gradient elution: 0～2.5min, 30%A～90%A; 2.5～3min, 90%A～95%A; 3～6min, 95%A; 6～8min, 95%A～30%A.
C) flow velocity: 0.25mL/min.
D) column temperature: 30 ℃.
E) sample size: 5 μ L.
(2) mass spectrum condition
A) ion gun: ESI.
B) ionization mode: negative ion mode.
C) capillary voltage: 1.5kV.
D) extraction voltage: 3V.
E) radio-frequency lens voltage: 0.5V.
F) ion source temperature: 150 ℃.
G) desolventizing temperature degree: 450 ℃.
H) data acquisition modes: multiple-reaction monitoring (MRM).
Table 1 mass spectrophotometry condition
3.2.2 the drafting of standard working curve
Accurately draw respectively the standard solution that the standard operation solution preparation becomes concentration to be 10 μ g/L, 50 μ g/L, 100 μ g/L, 250 μ g/L, 500 μ g/L, inner mark solution concentration is 50 μ g/L.Draw respectively accurately 5 μ L and inject liquid chromatography-series connection quadrupole mass spectrometers, according to being tested under above-mentioned analysis condition, the ratio of peak area of quota ion of take is ordinate, and the concentration corresponding with it is horizontal ordinate, the drawing standard working curve.
3.3 blank test
Except not adding sample, all by above-mentioned steps, undertaken.
4, result is calculated
Result is calculated by formula (1), and result of calculation retains two-decimal:
In formula:
The massfraction of W---nonyl phenol in cosmetic, unit is every kilogram (mg/kg) of milligram;
The concentration of nonyl phenol in c---the sample solution found from standard working curve, 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, get series of standards solution 10 μ g/L, 50 μ g/L, 100 μ g/L, 250 μ g/L, 500 μ g/L, ratio (Y-axis) with the peak area of nonyl phenol and internal standard compound is mapped to corresponding nonyl phenol concentration (X-axis), result shows, nonyl phenol concentration is in 10 μ g/L～500 μ g/L scopes, the linear equation of nonyl phenol is Y=1.21X+1.76, and linearly dependent coefficient r=0.9996 is the good linear relation.When the nonyl phenol in sample surpasses this range of linearity, can suitably add the extension rate of large sample.
5.2 the detection limit of method
Through to the laboratory experiment of the method for inspection, result shows, the mensuration lower bound (S/N=10) of method is 0.2mg/kg.
6, the recovery of method and precision
The experiment of this method recovery, by the interpolation situation in common cosmetics, has been set three and has been added concentration, by the determined experiment condition of this method, each is added to concentration and carry out 6 experiments, and the nonyl phenol recovery is 83.1%～103.0%; Indoor Precision Experiment (n=6) records relative standard deviation 2.75%～9.24%.The results are summarized in table 2-5.
Table 2 cream kind sample recovery rate and Precision Experiment result
Table 3 aqua class sample recovery rate and Precision Experiment result
Table 4 loose powder class sample recovery rate and Precision Experiment result
Table 5 lipstick class sample recovery rate and Precision Experiment result
7, conclusion
Comprehensive above-mentioned situation, the recovery of this method of inspection, all technicals 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 the present invention sets up is easy and simple to handle, result is accurate, can be used for the check of nonyl phenol in cosmetic.
Emphasis of the present invention is optimized above-mentioned experiment condition:
1, the selection of extracting method
1.1 extract the selection of solvent
For dissimilar cosmetics, selecting cream kind, loose powder class, aqua class, lipstick class cosmetics is research object.Investigated respectively the mixed solution of methyl alcohol, absolute ethyl alcohol and methylene chloride of methyl alcohol, absolute ethyl alcohol and different proportion as the extraction effect that extracts solution.Result shows, for cream kind, loose powder class, aqua class cosmetics, uses methyl alcohol and methylene chloride mixed solution (8: 2, volume fraction) as extraction effect the best of extracting solvent; For lipstick class cosmetics, use the extraction effect of absolute ethyl alcohol and methylene chloride mixed solution (8: 2, volume fraction) best.
1.2 the selection of extraction time
In order to obtain high as far as possible extraction efficiency and to reduce operation steps, in experiment, adopt ultrasonic extracting mode to be extracted sample.Having investigated respectively extraction time is the extraction effect under 15min, 20min, 25min, 30min, the ultrasonic extraction of 35min, 40min.Result shows, ultrasonic extraction 30min can realize that nonylphenol extracts fully.
2, the selection of Solid-Phase Extraction condition
According to bibliographical information, nonyl phenol is at C
18show good reverse-phase chromatography retention behavior on solid-phase extraction column, effect of extracting is better.In addition, Oasis HLB solid-phase extraction column is a kind of solid-phase extraction column based on the reverse-phase chromatography retention mechanism, and it has the C of ratio
18the adsorption capacity that solid-phase extraction column is higher and the wider advantages such as the pH scope of application.With Oasis HLB (6mL, 200mg) be solid-phase extraction column, investigated respectively the eluting solvent of different mixing: methyl alcohol, acetone-methyl alcohol mixed solution (1: 9, volume fraction), acetone-methyl alcohol mixed solution (3: 7, volume fraction), acetone-methyl alcohol mixed solution (5: 5, volume fraction), acetone-methyl alcohol-ethyl acetate mixture (4: 4: 2, volume fraction), acetone-methyl alcohol-ethyl acetate-formic acid (4: 4: 2: 0.1, volume fraction) the wash-out recovery, found that use acetone-methyl alcohol-ethyl acetate mixture (4: 4: 2, volume fraction) wash-out 6mL obtains the best recovery.
The Solid-Phase Extraction condition is as follows: first adopt 6mL methylene chloride and the activation of 6mL methyl alcohol, the 6mL water balance, the 2mL sample solution is with 1mL/min flow velocity loading, use 3mL methanol-water mixed solution (3: 7, volume fraction) clean, acetone-methyl alcohol-ethyl acetate mixture (4: 4: 2, volume fraction) at twice, each 3mL wash-out.The gained eluent slowly dries up with nitrogen, uses the 2mL methanol constant volume, through filtering with microporous membrane, for liquid phase chromatogram-series connection quadrupole rod mass spectroscopy.
3, the optimization of chromatographic condition
In LC-MS analysis, mobile phase composition not only affects chromatographic peak profile and the degree of separation of target compound, also can affect its Ionization Efficiency and detection sensitivity.Experiment, in satisfied chromatographic resolution preferably, has been investigated the impact of methanol-water and acetonitrile-water mobile phase system nonylphenol degree of ionization.Result shows, the instrumental response value of methanol-water mobile phase is higher than the acetonitrile-water mobile phase.Further comparative studies add respectively the impact of the volatility additives such as 0.1% ammoniacal liquor, 5mmol/L ammonium formate, 5mmol/L ammonium acetate in the methanol-water mobile phase.Result shows, methyl alcohol-0.1% ammonia spirit of usining has obtained optimum chromatographic resolution effect and mass signal response as mobile phase.With hydroxyl, at negative ion electrospray, in solution under pattern, can ionize out a hydrogen ion due to nonyl phenol, while adding certain alkaline matter (as ammoniacal liquor) in mobile phase, will promote the ionization of target compound, thereby improve its Ionization Efficiency.Further investigated the impact of the ammoniacal liquor addition of different proportion, the addition of ammoniacal liquor changes to 0.5% result from 0.05% and shows, 0.1% ammoniacal liquor is optimum addition.
4, the optimization of mass spectrum condition
The chemi-ionization character that there is phenolic hydroxyl group according to the phenols environmental estrogens, select ESI-as ionization mode, adopt flow injection pump continuous sample introduction mode to carry out the optimization of mass spectrum condition, experimental result shows, nonyl phenol, under ion gun ESI-ionization mode, can obtain more abundant [M-H]
-parent ion.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 is optimized to selection, determine quota ion and auxiliary qualitative ion, by optimizing capillary voltage, one-level taper hole voltage, secondary taper hole voltage, radio-frequency lens voltage, collision energy, the mass spectrum parameters such as mass resolution, make the quasi-molecular ion of nonyl phenol and the ion pair intensity of feature fragmention generation reach maximum, high performance liquid chromatography and triple quadrupole bar mass spectrometer is online, to ion source temperature, desolventizing temperature degree and flow, the taper hole airshed is optimized, make the Ionization Efficiency of test substance in sample liquid reach best.
Above-described embodiment is described the preferred embodiment of the present invention; not 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 a nonyl phenol in cosmetic is characterized in that: comprise the following steps:
(1) sample pretreating: take the about 0.5g of cosmetics sample, be placed in 50mL tool plug conical flask, add mark storing solution in 50 μ L, add again 10mL methyl alcohol or absolute ethyl alcohol and methylene chloride mixed solution, ultrasonic extraction 30min in ultrasonic cleaner, extract is moved in centrifuge tube, at the centrifugal 15min of 5000r/min speed, get supernatant 2mL after centrifugal, nitrogen slowly blows near dry, dissolve with 30% methanol aqueous solution vortex again, adopt 6mL methylene chloride and the activation of 6mL methyl alcohol, the isorrheic HLB Solid-Phase Extraction of 6mL column purification through in advance; The 2mL sample solution, with 1mL/min flow velocity loading, is used the 3mL30% methanol aqueous solution to clean, the mixed solution of acetone-methyl alcohol that volume fraction is 4:4:2-ethyl acetate, at twice, each 3mL wash-out; The gained eluent slowly blows near dry with nitrogen, uses the 2mL methanol constant volume, through filtering with microporous membrane, for liquid chromatography-tandem mass spectrometry, measures; Described methyl alcohol or absolute ethyl alcohol with the mixed volume ratio of methylene chloride mixed solution are: methyl alcohol or absolute ethyl alcohol: methylene chloride=8:2;
(2) measure: adopt liquid chromatography-mass spectrography/mass spectrometry method, wherein liquid phase chromatogram condition is: flow velocity: 0.25mL/min; Column temperature: 30 ℃; Sample size: 5 μ L; The mass spectrum condition is: capillary voltage: 1.5kV; Extraction voltage: 3V; Radio-frequency lens voltage: 0.5V; Ion source temperature: 150 ℃; Desolventizing temperature degree: 450 ℃; Liquid chromatography adopts methyl alcohol-0.1% ammonia spirit as mobile phase;
(3) drawing standard working curve: accurately draw respectively the standard solution that the standard operation solution preparation becomes concentration to be 10 μ g/L, 50 μ g/L, 100 μ g/L, 250 μ g/L, 500 μ g/L, inner mark solution concentration is 50 μ g/L; Draw respectively accurately 5 μ L and inject liquid chromatography-series connection quadrupole mass spectrometers, according to being tested under above-mentioned analysis condition, the ratio of peak area of quota ion of take is ordinate, and the concentration corresponding with it is horizontal ordinate, the drawing standard working curve.
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| CN105223264B (en) * | 2015-09-21 | 2017-12-29 | 广东联捷生物科技有限公司 | A kind of simulation internal standard method, apparatus of mass spectrum quantitative analysis and application |
| CN105301143A (en) * | 2015-11-30 | 2016-02-03 | 中国包装科研测试中心 | Method for detecting nonyl phenol in food packing material |
| CN106841448A (en) * | 2017-02-17 | 2017-06-13 | 孙丽 | A kind of detection method for polluting phenolic compound |
| CN111912930B (en) * | 2020-07-10 | 2021-05-25 | 甘肃省药品检验研究院 | Method for simultaneously determining 10 phthalic acid esters in aromatic cosmetics |
| CN113504322B (en) * | 2021-06-29 | 2023-04-28 | 暨南大学 | Multi-component high-throughput analysis method for plastic additive |
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