CN110174488B - Method for detecting allergen in cosmetics - Google Patents
Method for detecting allergen in cosmetics Download PDFInfo
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- CN110174488B CN110174488B CN201910495828.1A CN201910495828A CN110174488B CN 110174488 B CN110174488 B CN 110174488B CN 201910495828 A CN201910495828 A CN 201910495828A CN 110174488 B CN110174488 B CN 110174488B
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- G—PHYSICS
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- 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
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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
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- G01N30/88—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86
Abstract
The invention provides a method for detecting allergen in cosmetics, which comprises the following steps: preparing a mixed standard solution of 56 allergen substances from a mixed solution of methanol and 2g/L ascorbic acid aqueous solution, wherein 7 groups of isomers such as eugenol, isoeugenol and the like are independently prepared into a single-standard solution, performing mass spectrometry in a two-stage mass spectrometry scanning mode of electrostatic field orbital trap high-resolution mass spectrometry, namely positive and negative ion one-stage mass spectrometry full scanning and data dependence, and acquiring accurate mass number, retention time and second-stage fragment ion information of first-stage parent ions to establish a high-resolution mass spectrometry database; extracting a sample to be detected by adopting a mixed solution of methanol and 2g/L ascorbic acid aqueous solution, carrying out mass spectrometry, establishing a screening and quantitative analysis method by utilizing a database and adopting Tracefinder software, and detecting the allergen substances in the sample. The method is quick, high in sensitivity and good in specificity.
Description
Technical Field
The invention belongs to the technical field of compound analysis and detection, and particularly relates to a method for detecting allergens in cosmetics.
Background
Cosmetics are indispensable daily necessities in human life. However, due to the allergen substances such as perfume, antiseptic and dye components contained in the cosmetics and the diversity and specificity of the human autoimmune system, consumers often suffer from skin and its accessory organs, so-called cosmetic skin diseases, due to the use of cosmetics. According to the monitoring result of Chinese cosmetics on the adverse reaction of human bodies, the following results are shown: in recent years, with the increase of the variety of cosmetics, the incidence of clinical cosmetic skin diseases has been increasing year by year, and it is counted that most of cosmetic allergy is caused by perfume, preservative and dye components. At present, the main detection methods aiming at the allergen components comprise liquid chromatography, gas chromatography-mass spectrometry and liquid chromatography-mass spectrometry, but the traditional detection methods have some problems in detection and analysis: (1) the anti-interference capability to the complex matrix is insufficient, and false positive often appears; (2) because different types of allergens have different chemical properties, an extraction method is often established only for a certain type of allergens, and a method for simultaneously extracting several types of allergens is not available; (3) researchers often set different instrument parameters aiming at different types of allergen substances, establish different instrument detection methods, and can not complete all component screening by one-time detection, so that the detection process is too complicated. Therefore, a rapid, accurate and high-flux detection method for effectively monitoring allergen substances in cosmetics is urgently needed to be established.
Disclosure of Invention
In view of the above, the present invention aims to provide a method for detecting allergens in cosmetics, which can be used for detecting 56 kinds of allergens in 3 kinds of perfumes, preservatives and hair dyeing components, and has the advantages of rapidness, high sensitivity and good specificity.
The technical scheme of the invention is as follows: a method for detecting allergen in cosmetic comprises the following steps:
(1) establishing an allergen database;
(2) processing a sample to be detected;
(3) and (3) detection: detecting by adopting ultra-high performance liquid chromatography-electrostatic field orbital trap high resolution mass spectrometry, wherein the ultra-high performance liquid chromatography conditions are as follows: a chromatographic column: ZORBAX Eclipse Plus C18; the mobile phase A is methanol, the mobile phase B is 5mmol/L ammonium acetate water solution, and the gradient elution procedure is carried out; the conditions of the mass spectrum are as follows: an electrospray ion source; scanning positive and negative ions; ion source temperature: 350 ℃; spraying voltage: the positive ion mode is 3.5kV, and the negative ion mode is 3.0 kV;
(4) establishing a qualitative screening method;
(5) and (4) establishing a quantitative analysis method.
The allergen is a spice allergen, a preservative allergen and a hair dyeing component allergen, and the spice allergen is limonene, benzyl alcohol, linalool, citronellol, geraniol, hydroxycitronellal, eugenol, isoeugenol, alpha-isomethyl ionone, lilial, lyral, hexyl cinnamaldehyde, benzyl benzoate, benzyl salicylate, benzyl cinnamate, amyl cinnamaldehyde, cinnamyl alcohol citral, cinnamaldehyde and coumarin; the antiseptic allergen is methylisothiazolinone, methylchloroisothiazolinone, diazolidinyl urea, methylparaben, ethylparaben, isopropyl paraben, propyl paraben, isobutyl paraben, butyl paraben, salicylic acid, benzoic acid, sorbic acid; the hair dyeing component allergen is resorcinol, toluene-2, 5-diamine sulfate, p-phenylenediamine, p-aminophenol, m-aminophenol, 2-amino-3-hydroxypyridine, 4-chlororesorcinol, 4-amino-2-hydroxytoluene, 2, 4-diaminophenoxyethanol hydrochloride, N-bis (2-hydroxyethyl) p-phenylenediamine sulfate, 2-chloro-p-phenylenediamine sulfate, 2-methylresorcinol, 6-amino-m-cresol, phenyl-methyl pyrazolone, 4-amino-3-nitrophenol, 4-amino-m-cresol, p-methyl aminophenol sulfate, 4-nitrophthaldiamine, 2, 6-diaminopyridine, 6-hydroxyindole, 2, 7-naphthalenediol, p-amino-phenoxyethanol hydrochloride, N-bis (2-hydroxyethyl) p-phenylenediamine sulfate, 2-chloro-p-phenylenediamine sulfate, 2-methylresorcinol, 6-, N-phenyl-p-phenylenediamine, 1, 5-naphthalenediol or 1-naphthol.
Preparing a mixed standard substance solution of the allergen substances by using methanol and 2g/L ascorbic acid aqueous solution at a ratio of 1: 1, v/v, preparing a single-standard solution by using isomers separately, and analyzing by adopting a positive and negative ion switching FullMS/ddMS2 scanning mode to obtain retention time, primary parent ion accurate mass number and secondary fragment ion accurate mass number of various allergen substances so as to construct an allergen substance database.
The step (2) is specifically that a sample to be detected is accurately weighed and is put into a centrifuge tube of 0.25g to 50mL, 25mL of methanol and 2g/L of ascorbic acid aqueous solution are added, the ratio is 1: 1, v/v, vortex is carried out for 1min, ultrasonic extraction is carried out for 15min, centrifugation is carried out for 5min at 10000r/min, supernatant is transferred and is filtered through a 0.22 mu m microporous membrane, and the sample is put on a machine for detection; the wax content is high, 5mL of n-hexane is added into a water-in-oil sample for uniform dispersion, and then vortex ultrasonic extraction is carried out.
Preferably, the liquid chromatography flow rate: 0.3 mL/min; column temperature: 30 ℃; gradient elution conditions: 0-1 min 10% A, 2-6 min 10% -50% A, 6-8 min 50% -60% A, 8-16 min 60% A, 16-18 min 60% -10% A, 18-20 min 10% -90% A, 20-26 min 90% A, 26-29 min 90% -10% A, 29-30 min 10% A.
The quantitative screening method comprises the following specific steps: after the established allergen database is imported by utilizing TraceFinder software, screening parameters (including retention time deviation set as 30s, mother ion accurate mass number mass deviation threshold set as 5ppm, fragment ion accurate mass number mass deviation threshold set as 10ppm) are set, a qualitative screening method is established, information obtained by a sample through high-resolution mass spectrometry is matched with related information of a spectrum library, and high-throughput screening confirmation of a target object is achieved.
The establishment of the quantitative analysis method comprises the following steps: and (3) establishing a quantitative analysis method by taking the primary allergen parent ions as quantitative ions, and quantifying by an external standard method.
The invention adopts a one-step method to extract 56 different types of allergens of spices, preservatives and hair dyeing groups, thereby greatly simplifying the pretreatment steps. The method adopts a high-resolution mass spectrum positive and negative ion switching mode for detection, and screening is completed by only one needle of a detection system, so that the method is simple, convenient and quick, the detection flux is improved, and more allergen types are covered; the established database has the accurate mass number of the parent ions and the information of the secondary fragment ions, the probability of false positive is reduced, and the qualitative screening and quantitative analysis method established by the high-resolution mass spectrometry has high accuracy and sensitivity.
Drawings
FIG. 1 is an extracted ion chromatogram of 56 allergens.
FIG. 2 is a secondary mass spectrum of 56 allergens.
FIG. 3 is a chromatogram and a secondary mass spectrum of 2-amino-3-hydroxypyridine and 2, 4-diaminophenoxyethanol hydrochloride detected in hair dye.
FIG. 4 is a chromatogram and a secondary mass spectrum of methylisothiazolinone and methylchloroisothiazolinone detected in the body wash.
Detailed Description
Example 1
The instrument comprises the following steps: obitrap high resolution mass spectrometer (ThermoFisher, USA); CR22G II high-speed refrigerated centrifuge (Hitachi, Japan).
Reagent: cinnamyl alcohol, cinnamyl aldehyde, methylisothiazolinone, 2-amino-3-hydroxypyridine, 4-amino-2-hydroxytoluene, 2, 4-diaminophenoxyethanol hydrochloride, N-bis (2-hydroxyethyl) p-phenylenediamine sulfate, 2-chloro-p-phenylenediamine sulfate, phenylmethylpyrazolone, 4-amino-3-nitrophenol, 4-nitrophthaldiamine, p-methylaminophenol sulfate, 6-hydroxyindole, N-phenyl-p-phenylenediamine, 2, 7-naphthalenediol, 1, 5-naphthalenediol are from Shanghai' an spectra, diazoalkyl ureas from Accustandard, USA, the remainder from Dr. Preparing a hair dyeing component standard stock solution toluene-2, 5-diamine sulfate and 2-chloro-p-phenylenediamine sulfate by adopting 2g/L ascorbic acid aqueous solution; preparing 2-nitro-p-phenylenediamine and toluene-3, 4-diamine with methanol, and preparing the rest standard substances with methanol-2 g/L ascorbic acid aqueous solution (50: 50, V/V); the perfume and preservative allergen standard stock solution is prepared from methanol. Methanol (chromatographically pure, merck, usa); n-hexane, ammonium acetate (chromatographically pure, CNW, germany).
The detection conditions of ultra-high performance liquid chromatography-high resolution mass spectrometry are as follows: (1) chromatographic conditions are as follows: a chromatographic column: ZORBAX Eclipse Plus C18(3.0 mm. times.100 mm, 1.8 μm); flow rate: 0.3 mL/min; column temperature: 30 ℃; sample introduction volume: 5 mu L of the solution; mobile phase: a is methanol, B is 5mmol/L ammonium acetate water solution, and the gradient elution condition is as follows: 0-1 min 10% A, 2-6 min 10% -50% A, 6-8 min 50% -60% A, 8-16 min 60% A, 16-18 min 60% -10% A, 18-20 min 10% -90% A, 20-26 min 90% A, 26-29 min 90% -10% A, 29-30 min 10% A. (2) Mass spectrum conditions: spraying voltage: the positive ion mode is 3.5kV, and the negative ion mode is 3.0 kV; ion source temperature: 350 ℃; temperature of transmission metal capillary: 320 ℃; sheath gas pressure: 35 arb; auxiliary gas pressure: 15 arb; scanning range (m/z): 50-750 Da; first-order mass spectrum full-scan resolution: r is 70000; AGC target: 3e 6; maximum injection time: 100 ms; data dependent secondary ion full scan resolution: r is 17500; stepped NCE: 20eV, 45eV, 70 eV; AGC target: e 5; maximum injection time: 50 ms; dynamic exclusion time: for 10 s.
Establishing an allergen database: the allergen mixed standard working solution is analyzed in a high-resolution mass spectrum positive and negative ion switching FullMS/ddMS2 scanning mode, the accurate mass number and retention time of parent ions of objects to be detected are determined through a primary full scanning mode, after the accurate mass number of the parent ions is obtained, a list of the objects to be detected is established, high, medium and low collision energy is set to 3, when the parent ions in the list are detected during scanning and the intensity of the parent ions reaches a set threshold value, secondary scanning is automatically started through the mass spectrum, the accurate mass number of secondary fragment ions is obtained, and the acquired accurate mass number, retention time and accurate mass number of the primary parent ions are summarized to construct an allergen database.
Screening database for 156 allergens in table
Establishment of quantitative analysis method and methodological verification
Taking primary parent ions as quantitative ions, and quantifying by an external standard method. Preparing a series of standard samples by using a blank matrix solution, drawing a standard curve after mass spectrometry, wherein the ordinate (Y) is the chromatographic peak area, the abscissa (X) is the mass concentration of a control solution, diluting the standard solution step by using the matrix blank solution, and the lowest concentration which can be detected by an instrument is the detection limit of the method.Blank samples of oil-in-water samples (emulsions) and water-in-oil samples (nourishing creams) with different matrixes are selected, and 3 adding experiments with different levels of low, medium and high are respectively carried out (n is 6). The results demonstrate that all perfume sensitising ingredients have a good linear relationship (R)2Greater than 0.99), the detection limit is 0.1-20 mug/g, the recovery rate of each target object is 85.1-109.9%, and the RSD is 3.1-9.9%. Therefore, the detection limit, the recovery rate and the precision of the established method can meet the detection requirement, and can be used for monitoring high-risk allergens in cosmetics.
Linear regression equation, correlation coefficient, linear range and detection limit for 256 allergens in table
Note: content of allergen (μ g/g) in cosmetic is mass concentration (μ g/L) of component to be measured/1000 obtained from standard curve
EXAMPLE 2 confirmation and quantitative analysis of actual sample screening
8 commercially available hair dyes and 15 cosmetics are measured according to the method determined by the text, detected components of spices, preservatives and dyes are consistent with label marking components, and the content of the detected components is less than the limit requirement in technical Specification for cosmetic safety (2015 edition) in China. The screening and confirmation processes of the compounds in the actual samples are introduced by taking two dye components of 2-amino-3-hydroxypyridine and 2, 4-diaminophenoxyethanol hydrochloride detected in a hair dye sample and methylisothiazolinone and methylchloroisothiazolinone detected in shower gel as examples. Firstly, carrying out FullMS/ddMS2 detection on a sample, comparing detection data with retention time, accurate mass number of parent ions and secondary fragment ions in a database through Trace Finder software, and carrying out rapid screening and confirmation; meanwhile, a quantitative method is established by directly utilizing the parent ions to carry out quantitative analysis on the screened target substances. Fig. 3 is a chromatogram and a secondary mass spectrum of extracted ions of 2-amino-3-hydroxypyridine (a and b) and 2, 4-diaminophenoxyethanol hydrochloride (c and d) in a hair dye sample, and fig. 4 is a chromatogram and a secondary mass spectrum of methylisothiazolinone (a and b) and methylchloroisothiazolinone (c and d) in a bath lotion, and it can be seen that the retention time of an allergen collected in the sample, the accurate mass numbers of parent ions and secondary fragment ions are substantially consistent with the retention time and the theoretical accurate mass numbers in table 1, and allergen components are present in the sample, so that the screening result is reliable.
Claims (4)
1. A method for detecting an allergen in a cosmetic, which is characterized by comprising the following steps: the method comprises the following steps:
(1) establishing an allergen database;
(2) processing a sample to be detected;
(3) and (3) detection: detecting by adopting ultra-high performance liquid chromatography-electrostatic field orbital trap high resolution mass spectrometry, wherein the conditions of the ultra-high performance liquid chromatography are as follows: a chromatographic column: ZORBAX Eclipse Plus C18; the mobile phase A is methanol, the mobile phase B is 5mmol/L ammonium acetate water solution, and the gradient elution procedure is carried out; the conditions of the mass spectrum are as follows: an electrospray ion source; scanning positive and negative ions; ion source temperature: 350 ℃; spraying voltage: the positive ion mode is 3.5kV, and the negative ion mode is 3.0 kV;
the allergen is perfume allergen, antiseptic allergen, and hair dyeing component allergen;
preparing a mixed standard substance solution of allergen substances by using methanol and 2g/L ascorbic acid aqueous solution at a ratio of 1: 1 and v/v, preparing a single-standard solution by using isomers separately, and analyzing by adopting a positive and negative ion switching FullMS/ddMS2 scanning mode to obtain retention time, accurate mass numbers of primary parent ions and secondary fragment ions of various allergen substances and construct an allergen substance database;
the step (2) is specifically that a sample to be detected is accurately weighed and is put into a centrifuge tube of 0.25g to 50mL, 25mL of methanol and 2g/L of ascorbic acid aqueous solution are added, the ratio is 1: 1, v/v, vortex is carried out for 1min, ultrasonic extraction is carried out for 15min, centrifugation is carried out for 5min at 10000r/min, supernatant is transferred and is filtered through a 0.22 mu m microporous membrane, and the sample is put on a machine for detection; the wax content is high, 5mL of n-hexane is added into a water-in-oil sample for uniform dispersion, and then vortex ultrasonic extraction is carried out;
the liquid chromatography flow rate in the step (3): 0.3 mL/min; column temperature: 30 ℃; gradient elution conditions: 0-1 min 10% A, 2-6 min 10% -50% A, 6-8 min 50% -60% A, 8-16 min 60% A, 16-18 min 60% -10% A, 18-20 min 10% -90% A, 20-26 min 90% A, 26-29 min 90% -10% A, 29-30 min 10% A;
the perfume allergen is limonene, benzyl alcohol, linalool, citronellol, geraniol, hydroxycitronellal, eugenol, isoeugenol, alpha-isomethylionone, lilial, lyral, hexyl cinnamaldehyde, benzyl benzoate, benzyl salicylate, benzyl cinnamate, amyl cinnamaldehyde, cinnamyl alcohol citral, cinnamaldehyde and coumarin;
the antiseptic allergen is methylisothiazolinone, methylchloroisothiazolinone, diazolidinyl urea, methylparaben, ethylparaben, isopropyl paraben, propyl paraben, isobutyl paraben, butyl paraben, salicylic acid, benzoic acid, sorbic acid;
the hair dyeing component allergen is resorcinol, toluene-2, 5-diamine sulfate, p-phenylenediamine, p-aminophenol, m-aminophenol, 2-amino-3-hydroxypyridine, 4-chlororesorcinol, 4-amino-2-hydroxytoluene, 2, 4-diaminophenoxyethanol hydrochloride, N-bis (2-hydroxyethyl) p-phenylenediamine sulfate, 2-chloro-p-phenylenediamine sulfate, 2-methylresorcinol, 6-amino-m-cresol, phenyl-methyl pyrazolone, 4-amino-3-nitrophenol, 4-amino-m-cresol, p-methyl aminophenol sulfate, 4-nitrophthaldiamine, 2, 6-diaminopyridine, 6-hydroxyindole, 2, 7-naphthalenediol, p-amino-phenoxyethanol hydrochloride, N-bis (2-hydroxyethyl) p-phenylenediamine sulfate, 2-chloro-p-phenylenediamine sulfate, 2-methylresorcinol, 6-amino-m-cresol, phenyl-methyl pyrazolone, 4-amino-3-nitrophenol, 4-amino-m-cresol, p-methyl aminophenol sulfate, 4-nitrophenol, 2, 6-diaminopyridine, 6-hydroxyindole, 2, 7-naphthalenediol, p-phenoxyethanol hydrochloride, p-phenylenediamine, m-phenylenediamine, p-cresol, and p-cresol, p-p, N-phenyl-p-phenylenediamine, 1, 5-naphthalenediol or 1-naphthol.
2. The detection method according to claim 1, wherein the parameters of the parent ion and the secondary fragment ion of the mass spectrum are as follows:
3. the test method according to claim 1, further comprising establishing a qualitative screening method: and (3) importing the database established in the step (1) by utilizing TraceFinder software, setting screening parameters, wherein the screening parameters comprise retention time deviation of 30s, a mass deviation threshold of the accurate mass number of the parent ions of 5ppm and a mass deviation threshold of the accurate mass number of the fragment ions of 10ppm, establishing a qualitative screening method, and matching information obtained by analyzing the sample by high-resolution mass spectrometry with related information of a spectrum library.
4. The method of claim 1, further comprising the step of establishing a quantitative analysis method comprising: and (3) establishing a quantitative analysis method by taking the primary parent ions as quantitative ions, and quantifying by an external standard method.
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| CN111007174A (en) * | 2019-12-24 | 2020-04-14 | 中检科健(天津)检验检测有限责任公司 | HPLC method for simultaneously detecting resorcinol and 2-nitro-p-phenylenediamine |
| CN111855789B (en) * | 2020-06-12 | 2024-04-09 | 交通运输部公路科学研究所 | Method for identifying blended asphalt |
| CN111812265B (en) * | 2020-07-10 | 2021-05-18 | 甘肃省药品检验研究院 | Detection method for simultaneously determining 32 dyes in hair dye |
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| CN113101378B (en) * | 2021-04-13 | 2021-11-16 | 黑龙江省医院 | Cosmetic allergen detection method and allergen patch kit |
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