CN104122359A - Method for simultaneously detecting 14 types of forbidden coloring agents in cosmetics - Google Patents
Method for simultaneously detecting 14 types of forbidden coloring agents in cosmetics Download PDFInfo
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Abstract
The invention provides a method for simultaneously detecting 14 types of forbidden coloring agents in cosmetics. The method comprises following detection steps: preparing a methanol-water ammonium acetate solution and an ammonium acetate solution; preparing a standard solution for drawing a standard curve; carrying out liquid chromatographic analysis; carrying out mass spectrum confirmation; preparing a sample solution; carrying out qualitative analysis; carrying out quantitative determination; and determining the content of a target object in the sample solution by using a standard curve external standard method, wherein the content (mg/g) of the target object in the sample solution is equal to (C*V/m)*10<-3>. The method has the advantages of simplicity and feasibility, low cost, high precision, and capability of simultaneously detecting the 14 types of forbidden coloring agents.
Description
Technical field
The present invention relates to a kind of detection method, particularly a kind of 14 kinds of methods that forbidding colorant detects simultaneously in cosmetics.
Background technology
Colorant (also claiming pigment), as one of cosmetic material, is widely used in cosmetics.The object that uses colorant in ordinary cosmetics is for making product painted, can also adjust the impact of some raw material on product shade, in order to distinguish different product varietys.In color make-up cosmetics, use the effect that beautifies, modifies of mainly playing.
Colorant can be divided into dyestuff and the large class of pigment two according to performance and coloring mode, and dyestuff is divided into again natural dye and synthetic dyestuffs, and pigment is divided into inorganic pigment and organic pigment.According to source mode, can be divided into natural colorant and the large class of synthetic coloring matter two.Wherein natural dye and inorganic pigment generally belong to natural colorant, and synthetic coloring matter comprises synthetic dyestuffs and organic pigment.Most synthetic coloring matter is many to be tended to human body to cause harm in various degree from coal tar product, for example, causes fecundity decline, monster, even brings out cancer, and some synthetic dyestuffs can cause photosensitized reaction.At present, cosmetics have become daily necessities for some, and for safety, many countries have all made relevant regulations to colorant used for cosmetic in the world.China " cosmetics health specification " (2007) is with reference to " European Union's regulatory affairs " and in conjunction with Chinese feature, and kind, usable range and restrictive condition to colorant used for cosmetic have all been made clear and definite regulation.
The colorant referring explicitly in Ministry of Public Health's " cosmetics health specification " (2007 editions) banned substance list comprises benzidion azo dyes (the 270th article), o-dianisidine based azo dyes (the 926th article), outside ortho-tolidine radical dye (the 931st article), also comprise 369-378 article totally 10 articles (relating to 13 kinds of colorants), the 310th article (the Sudan I) and the 451st article (disperse yellow 3).The result that provides assessment according to toxicological experiment data shows, uses forbidding colorant can cause allergic, toxic reaction, even bring out cancer in cosmetics.
" cosmetics health specification " (2007 editions), although provided the colorant stock chart of forbidding, do not provide the many colorants of cosmetics and detect corresponding standard detecting method simultaneously, and this just to production supervision and product quality to ensure to have caused technical difficulty.Therefore, be necessary to develop quick, accurate, sensitive detection method, for the quality monitoring of cosmetics provides effective technical support and powerful guarantee.
At present, to the detection of colorant in cosmetics, there is the method for bibliographical information to comprise both at home and abroad: thin-layered chromatography, Micellar Electrokinetic Chromatography, high performance liquid chromatography-tandem mass method (HPLC-MS/MS), high performance liquid chromatography-UV, visible light detection method (HPLC-UV) and high performance liquid chromatography-Diode array detection (HPLC-DAD).During reading up the literature, institute relates to altogether 11 kinds of (SudanⅣs (C.I. 26105) of forbidding colorant, acid violet 49 (C.I. 42640), the Sudan's indigo plant 2 (C.I. 61554), solvent red 49 (C.I. 45170:1), alkaline purple 1 (C.I. 42535), pigment orange 5 (C.I. 12075), quinoline yellow 6(C.I. 13065), paratonere 53:1(C.I. 15585:1), Sudan II (C.I. 12140) and rhodamine B (C.I. 45170), single kind method relates at most 7 kinds of (SudanⅣs (C.I. 26105) of forbidding colorant, acid violet 49 (C.I. 42640), the Sudan's indigo plant 2 (C.I. 61554), solvent red 49 (C.I. 45170:1), alkaline purple 1 (C.I. 42535), pigment orange 5 (C.I. 12075), paratonere 53(C.I. 15585)).
Sample pre-treatments adopts the methods such as solvent extraction, Solid-Phase Extraction, liquid-liquid extraction mostly.Chromatographic resolution all adopts conventional C18 chromatographic column, and mobile phase is the gradient elution program of multiplex methyl alcohol or acetonitrile and phosphate or ammonium acetate buffer, and also useful TBAH is done the chromatogram that ion-pairing agent strengthens water-soluble object and retained.Detect 240 nm of employing of wavelength, 480 nm, 520 nm equiwavelengths more.LC-MS is also very not general at present in the application of colorant detection field.
In examination criteria field, cosmetics colorant detects and there is no any existing national standard at present.GB plan 20090914-T-607 " the mensuration high performance liquid chromatography of 4 kinds of forbidding colorants such as rhodamine B in cosmetics ", relates to 4 kinds of forbidding colorants, at present in the standard declaration stage, not yet formally issues.State Food and Drug Administration issues in cosmetics detection method; [2012] No. 13 annex 15 methods of state food medicine prison guarantorizations, relate to 5 kinds and forbid colorant (quinoline yellow 6(C.I. 13065), pigment orange 5s (C.I. 12075), paratonere 53:1(C.I. 15585:1), Sudan II (C.I. 12140) and SudanⅣ (C.I. 26105)).Find by literature research, existing detection method and means are difficult to meet current cosmetic field forbidding colorant are used to safe quality monitoring requirement.In cosmetics, forbidding the detection of colorant polycomponent remains in very large research blank.This make cosmetics especially the quality safety of makeup cosmetic cause social extensive concern.For this reason, accelerate to forbid in cosmetics the detection method exploitation of colorant, meet growing cosmetics safety supervision needs, meaning is particularly great.
Summary of the invention
The object of this invention is to provide a kind of simple and easy to do, 14 kinds of forbidding colorants and can detect simultaneously, increase work efficiency, reduce by 14 kinds of methods that forbidding colorant detects simultaneously in the cosmetics of testing cost, overcome the deficiencies in the prior art.
14 kinds of methods that forbidding colorant detects simultaneously in cosmetics of the present invention, described colorant is: acridine yellow, solvent blue 35, solvent red 49, acid violet 49, tetramethyl phosphonium chloride Pararosaniline, pigment orange 5, paratonere 53, chlorination pentamethyl Pararosaniline, Sudan II, chlorination hexamethyl Pararosaniline, SudanⅣ, rhodamine B, disperse yellow 3, S Ⅰ; It is characterized in that: detecting step is as follows:
(1) preparation of salt solusion
Ammonium acetate is joined in the mixed solution of first alcohol and water, the volume ratio of methyl alcohol and water is 1 ︰ 1, obtains methanol-water ammonium acetate solution after ammonium acetate fully dissolves, and ammonium acetate concentration is 50 ~ 250 mmol/L;
Ammonium acetate is added to the water and is fully dissolved, make the ammonium acetate solution that concentration is 10～50 mmol/L;
(2) preparation of standard solution
Equivalent takes acridine yellow respectively, solvent blue 35, solvent red 49, acid violet 49, tetramethyl phosphonium chloride Pararosaniline, pigment orange 5, paratonere 53, chlorination pentamethyl Pararosaniline, Sudan II, chlorination hexamethyl Pararosaniline, SudanⅣ, rhodamine B, disperse yellow 3, S Ⅰ is also placed in same volumetric flask, be that the methyl alcohol of 1 ︰ 1 and tetrahydrofuran solution fully dissolve and be settled to groove by volume ratio, be mixed with the mixed standard solution that each object concentration is 20 μ g/mL, be respectively 5 by methyl alcohol and a series of each object concentration of tetrahydrofuran solution stepwise dilution preparation that volume ratio is 1 ︰ 1 again, 2, 1, 0.5, the mixed standard solution of 0.2 μ g/mL, for the drafting of typical curve,
(3) preparation of sample solution:
Take cosmetic sample to be measured and be placed in centrifuge tube, in centrifuge tube, add tetrahydrofuran, the amount ratio of cosmetics to be measured and tetrahydrofuran is 0.2 g ︰ 6 mL, vortex ultrasonic 10 min, make sample dispersion or with 80 DEG C of water-baths suitable heating 1 ~ 2 min, extract object, to the methanol-water ammonium acetate solution that adds (1) step gained in centrifuge tube, the amount ratio of tetrahydrofuran and methanol-water ammonium acetate solution is 6 mL ︰ 4 mL, make to extract solution and be settled to tetrahydrofuran and methanol-water ammonium acetate solution sum, vortex mixes rear ultrasonic 10 min, then in centrifugal 10 min of 5000 r/min, get clarification extract, to be measured after 0.45 μ m filtering with microporous membrane,
(4) liquid-phase chromatographic analysis, reference conditions are as follows:
Chromatographic column: poroshell 120 EC-C
18, 2.7 μ m, 3.0 mm × 100 mm or quite person; Column temperature: 35 DEG C; Flow velocity: 0.5 mL/min; Sample size: 2 μ L; With DAD detecting device detect wavelength: 416 nm, 514 nm, 590 nm; Mobile phase: A is 10～50 mmol/L ammonium acetate solutions that (1) step makes, B acetonitrile, gradient elution;
(5) mass spectrum confirmation, reference conditions are as follows:
Liquid phase chromatogram condition: chromatographic column: poroshell 120 EC-C
18, 2.7 μ m, 3.0 mm × 100 mm or quite person; Flow velocity: 0.5 μ L/min; Sample size: 2 μ L; Mobile phase: A aqueous phase solution, negative mode is 10mmol/L ammonium acetate solution; Holotype is 0.33 ‰ formic acid solution, B organic phase solution, and negative mode is acetonitrile and methyl alcohol, the volume ratio of acetonitrile and methyl alcohol is 6 ︰ 4; Holotype is acetonitrile, gradient elution;
Mass spectrum reference conditions: ion gun: electron spray ionisation source (ESI source); Detection mode: multiple-reaction monitoring (MRM); Atomization gas: nitrogen, 35 Psi; Dry gas: nitrogen, flow velocity 10 L/min, temperature: 350 DEG C; Collision gas: nitrogen; Collision voltage: 380V; Capillary voltage: 4000 V; Other mass spectrum parameters are as follows:
The mass spectrophotometry reference parameter of object
;
(6) qualitative analysis
The sample solution that the standard solution of respectively (2) step being obtained and (3) step obtain is analyzed according to optimum liquid phase analysis reference conditions described in (4) step, the liquid chromatography separation spectrogram of the sample solution obtaining under identical liquid phase chromatogram condition is separated to spectrogram with the liquid chromatography of standard substance to be compared, if there is the chromatographic peak that retention time is consistent with the retention time of certain standard substance in sample spectrogram, and the ultraviolet absorpting spectrum after its background correction is consistent with the ultraviolet absorpting spectrum of this standard substance, can tentatively assert and in sample, have this material; Be defined as positive sample through liquid phase chromatography, must carry out mass spectrophotometry through the mass spectrum confirmation reference conditions described in (5) step and further confirm;
(7) quantitative measurement
Pipette (2) step series standard solution, carry out efficient liquid phase chromatographic analysis according to (4) step chromatographic condition, taking series standard concentration of polymer solution as horizontal ordinate, peak area is ordinate, production standard curve; Acridine yellow and disperse yellow 3 quantitatively calculate according to the uv absorption under 416 nm, paratonere 53, solvent red 49, pigment orange 5, S Ⅰ, Sudan II, SudanⅣ, alkaline purple 10 quantitatively calculate according to the uv absorption under 514 nm, and acid violet 49, tetramethyl phosphonium chloride Pararosaniline, chlorination pentamethyl Pararosaniline, chlorination hexamethyl Pararosaniline, solvent blue 35 quantitatively calculate according to the uv absorption under 590 nm;
Be the hydrochloride of solvent red 49 in view of alkaline purple 10 is real, identical with the appearance time of solvent red 49 in the method, it is alkaline purple 10 or solvent red 49 that method cannot be differentiated.Unless known, otherwise be unified test result, suggestion selective solvent red 49 is as standard substance, and test result is reported the content in solvent red 49;
The content of object in sample solution, definite by typical curve external standard method; In cosmetic sample, the content of object calculates by " formula (1) ";
In formula:
c---the mass concentration of object in the sample solution calculating from typical curve, μ g/mL;
V---press the tested sample liquid cumulative volume of extension rate conversion, mL;
M---take the quality of sample, g;
Result of calculation retains three position effective digitals;
If the mass concentration of object exceedes the upper limit of the calibration curve range of linearity in solution to be measured, after must suitably diluting liquid to be measured, redeterminate.
The present invention is to 369th ~ 378 articles of " cosmetics health specification " (2007 editions) banned substance lists, article 310,14 kinds of regulation forbidding colorant (acridine yellows and in the 451st article, acid violet 49, paratonere 53, solvent red 49, chlorination pentamethyl Pararosaniline, tetramethyl phosphonium chloride Pararosaniline, disperse yellow 3, chlorination hexamethyl Pararosaniline, pigment orange 5, S Ⅰ, Sudan II, solvent blue 35, SudanⅣ, alkaline purple 1 0) simultaneously assay method be studied, develop the efficient liquid-phase chromatography method that simultaneously detects 14 kinds of forbidding colorants in cosmetics.And developed the mass spectrum screening method of these 14 kinds forbidding colorants, increase the accuracy of method.
Through the screening in experimentation, obtain good extraction solvent system, the sample solution after extracting does not need further purification process process, makes extracting method simple, has simplified the processing procedure of sample.Chromatographic column (poroshell 120 EC-C that choice for use is novel
18) 14 kinds of forbidding colorants are carried out to liquid phase separation, in 15 minutes, can complete the baseline separation of 14 kinds of objects.Adopt DAD detecting device to realize and analyze 14 kinds of forbidding colorants in mensuration cosmetics, the analysis time of having saved sample simultaneously.Conventional, the simple liquid phase flow phase system that adopt, make analysis operation simple.The method is applicable to the quantitative measurement of 14 kinds of forbidding colorants in the cerul classes such as lipstick, nail oils and loose powder class cosmetics.
The present invention is to 369th ~ 378 articles of " cosmetics health specification " (2007 editions) banned substance lists, article 310,14 kinds of regulation forbidding colorant (acridine yellows and in the 451st article, acid violet 49, paratonere 53, solvent red 49, chlorination pentamethyl Pararosaniline, tetramethyl phosphonium chloride Pararosaniline/disperse yellow 3, chlorination hexamethyl Pararosaniline, pigment orange 5, S Ⅰ, Sudan II, solvent blue 35, SudanⅣ, alkaline purple 1 0) simultaneously assay method be studied, develop the efficient liquid-phase chromatography method that simultaneously detects 14 kinds of forbidding colorants in cosmetics.And developed the mass spectrum screening method of these 14 kinds forbidding colorants, increase the accuracy of method.
Through the screening in experimentation, obtain good extraction solvent system, the sample solution after extracting does not need further purification process process, makes extracting method simple, has simplified the processing procedure of sample.Chromatographic column (poroshell 120 EC-C that choice for use is novel
18) 14 kinds of forbidding colorants are carried out to liquid phase separation, in 15 minutes, can complete the baseline separation of 14 kinds of objects.Adopt DAD detecting device to realize and analyze 14 kinds of forbidding colorants in mensuration cosmetics, the analysis time of having saved sample simultaneously.Conventional, the simple liquid phase flow phase system that adopt, make analysis operation simple.The method is applicable to the quantitative measurement of 14 kinds of forbidding colorants in the cerul classes such as lipstick, nail oils and loose powder class cosmetics.
That this method has advantages of is simple and easy to do, 14 kinds of colorants can detect simultaneously, time saving and energy saving, cost is low.
Embodiment
The optimization of embodiment 1 experiment condition
(1) optimization of sample pre-treatments condition
Consider the dispersiveness of cosmetic sample and the dissolubility of object, this experiment is attempted using tetrahydrofuran as dispersion solvent dispersed sample and solubilized target composition, and then add the methanol aqueous solution of polarity to increase the polarity of system, nonpolarity element (as matrix such as macromolecular excipient in the cerul in lipstick and nail polish) in sample is separated out, to avoid the infringement of these materials to reverse-phase chromatographic column, extend the serviceable life of chromatographic column.And adding of ammonium acetate can effectively improve part object and cause yield phenomenon on the low side because of matrix absorption.Therefore, experiment is final to be determined taking tetrahydrofuran, methyl alcohol and water volume ratio as 3:1:1, and ammonium acetate concentration is that the dicyandiamide solution of 20 mmol/L is as extraction solution.
(2) optimization of liquid phase chromatogram condition
1. to select suitable chromatographic column be the key of analytical approach in the selection of chromatographic column.C18 chromatographic column is the most frequently used chromatographic column in laboratory, and therefore this method is preferentially selected C18 chromatographic column.Through investigating the separating effect of 14 kinds of target components in C18 chromatographic column, result shows that tetramethyl phosphonium chloride Pararosaniline, chlorination pentamethyl Pararosaniline, chlorination hexamethyl Pararosaniline retained strong in C18 chromatographic column, and the serious broadening of chromatographic peak peak shape of chlorination hexamethyl Pararosaniline, overlapping serious with other compound chromatographic peaks.Add TBAH (TBA) in water after, this problem improves, and the retention time of 3 chromatographic peaks 10～20min that moved forward.In view of the end-blocking effect of TBA to C18 post silicon hydroxyl, infer that causing compound to retain too strong reason may be that object is with due to fixing interaction of going up mutually between remaining silicon hydroxyl.Consider some Novel chromatographic columns of in recent years releasing, because adopted new bonding techniques, after Silica Surface overlie polymer material, can significantly reduce the effect of exposed silicon hydroxyl to target compound.Aiglent poroshell 120 EC-C18 are one of this kind of novel chromatographic column.For this reason, experiment attempts using this chromatographic column for improving the chromatographic resolution of 14 kinds of target compounds.Identical with the appearance time of solvent red 49 in view of rhodamine B under same chromatographic condition, it is rhodamine B or solvent red 49 that method cannot be differentiated, and be used as a kind of compound carries out stratographic analysis to these two compounds in fact.Therefore 14 kinds of object reality can only show at most 13 chromatographic peaks.Studies show that, under the chromatographic condition of optimizing, in this chromatographic column, can realize the chromatographic resolution of 14 objects and obtain the chromatographic peak of 13 baseline separation.Selecting Aiglent poroshell 120 EC-C18 for this this experiment is final is analysis chromatographic column.
2. in mobile phase the optimization of eluting solvent and modifier to have compared water be mobile phase A phase (weak eluting solvent), and Mobile phase B phase (strong eluting solvent) adopts respectively methyl alcohol, acetonitrile and during containing the methanol solution of isopropyl alcohol, the impact of gradient elution on the behavior of 14 kinds of target compound chromatographic resolution.Result shows, is optimizing under chromatographic condition, and acetonitrile is as Mobile phase B phase, and the peak shape of each chromatographic peak preferably and substantially can reach baseline separation.For this reason, the final selection of this experiment acetonitrile is strong eluting solvent.
In order to obtain good separating effect, in water, add a series of modifier, obtain different water conditions.Each water condition is as follows: a. 20 mmol/L ammonium acetate-5 mmol/LTBA solution (with vinegar acid for adjusting pH to 8.0); B. 50 mmol/L ammonium acetate solutions (with ammoniacal liquor adjusting pH to 8.0); C. 30 mmol/L ammonium acetate solutions (with ammoniacal liquor adjusting pH to 8.0); D. 10 mmol/L ammonium acetate solutions (with ammoniacal liquor pH to 8.0); E. 10 mmol/L ammonium acetate solutions (containing 0.03% formic acid); F. 10 mmol/L ammonium acetate solutions; G: water.Compare the chromatographic resolution behavior of 14 kinds of target compounds under the above-mentioned water condition.Result demonstration, under b, c, d, f condition, 14 kinds of target compounds all can obtain excellent chromatographic resolution degree, and each chromatogram peak base separates, and is evenly distributed on whole chromatogram.Consider under f condition that ammonium acetate concentration is minimum and without regulating pH value, mobile phase preparation is convenient, low salt concn is less to chromatograph and chromatographic column infringement, therefore determines by f condition to be that 10 mmol/L ammonium acetate solutions are as water, to obtain best chromatographic resolution.
3. the optimization that ultraviolet detects wavelength, by the analysis at 190～600 nm ultraviolet scanning spectrums to all objects, is found the absorption maximum of 14 objects, mainly concentrates near 410,500,590 nm.After optimizing, determine that run-down gathers the liquid chromatography separating spectrum under 3 wavelength of 416,514,590 nm simultaneously.Wherein acridine yellow and disperse yellow 3 are larger in 416nm uv absorption, disturb littlely, therefore determine that the detection wavelength of these 2 objects is 416nm.The retention time of acid violet 49 is short, easily disturbed by other materials,, interference large in its uv absorption of 590nm lacked, tetramethyl phosphonium chloride Pararosaniline, chlorination pentamethyl Pararosaniline, chlorination hexamethyl Pararosaniline, solvent blue 35, in 590 nm uv absorption maximums, therefore adopt the detection wavelength of 590 nm to these 5 kinds of compounds in addition.All the other 7 kinds of compounds can obtain best uv absorption at 514 nm, therefore determine the detection wavelength that adopts 514 nm.
Chromatographic condition with above-mentioned optimization carries out liquid chromatography separation to object, and result shows, 14 kinds of objects (13 chromatographic peaks) can obtain baseline separation (see figure 1) completely in 15min.In view of method cannot be differentiated rhodamine B and solvent red 49, unless therefore known, otherwise be unified test result, suggestion selective solvent red 49 is as standard substance, and test result is reported the content in solvent red 49.
Embodiment 2 the inventive method confirmatory experiments
(1) range of linearity and related coefficient
Pipette the serial mixed standard solution that concentration is respectively 2.5,2,1,0.5,0.2 μ g/mL, analyze according to optimizing chromatographic condition, taking the mass concentration of series standard solution as horizontal ordinate, peak area is ordinate, carries out linear regression analysis.Equation of linear regression and the related coefficient of each object are as shown in table 1.Result of study shows: each object has good linear relationship within the scope of 0.2～20 μ g/mL, and related coefficient is all greater than 0.999.
Linear equation, related coefficient, detection limit and the quantitative limit of 14 kinds of forbidding colorants of table 1
(2) recovery and lower limit of quantitation
To not containing quantitatively adding mixed standard solution in the blank sample of target substance, after processing by pre-treating method, detect, calculate signal to noise ratio (S/N ratio) (S/N).Taking S/N=3 as detection limit, taking S/N=10 as lower limit of quantitation, determine detection limit and the lower limit of quantitation of each object.Concrete outcome is in table 1.What 14 kinds of objects of result demonstration were minimum is quantitatively limited to 3 μ g/g, detects and is limited to 1 μ g/g; The highest 10 μ g/g that are quantitatively limited to, detect and are limited to 3 μ g/g.Can meet daily detection demand.14 kinds of objects are carried out to recovery testu respectively under 3 concentration levels of 10,100,500 μ g/g, and each horizontal parallel is measured 6 samples, and its recovery and relative standard deviation are in table 2.As shown in Table 2, the recovery of standard addition of each object is 90.2% ~ 109.9%, and relative standard deviation (RSD) is all lower than 10%.Method has shown the good recovery and precision.
Recovery of standard addition and the relative standard deviation of 14 kinds of forbidding colorants of table 2
Embodiment 3 lipstick class actual samples detect
(1) preparation of salt solusion
Methanol-water ammonium acetate solution: get ammonium acetate 0.77 g, join in 100 mL water and fully dissolve, then add methyl alcohol 100mL, fully mix, making ammonium acetate concentration is the methanol-water ammonium acetate solution of 50 mmol/L.
Ammonium acetate solution: get ammonium acetate 0.77g, join in 500 mL water and fully dissolve, make the ammonium acetate solution that concentration is 20 mmol/L.
(2) preparation of standard inventory solution
Take pigment orange 5, each 10 mg(of disperse yellow 3 are accurate to 0.1 mg), after dissolving with tetrahydrofuran and ethanol respectively, be settled to 50 mL and be mixed with the standard inventory solution that concentration is 0.2 mg/mL.Take each 10 mg(of paratonere 53 and SudanⅣ and be accurate to 0.1 mg), after dissolving with dimethyl sulfoxide (DMSO) and tetrahydrofuran respectively, be settled to 10 mL, being mixed with concentration is the standard inventory solution of 1 mg/mL.Take each 10 mg(of all the other 9 kinds of standard substances (except pigment orange 5, disperse yellow 3, paratonere 53, SudanⅣ, alkaline purple 1 0) and be accurate to 0.1 mg), after dissolving with methyl alcohol respectively, be settled to 10 mL, be mixed with the standard inventory solution that each object concentration is 1 mg/mL.Be the hydrochloride of solvent red 49 in view of alkaline purple 10 is real, identical with the appearance time of solvent red 49 under same chromatographic condition, it is alkaline purple 10 or solvent red 49 that method cannot be differentiated, can be according to the preparation of choosing any one kind of them of reference material situation while therefore preparing standard reserving solution.
(3) preparation of standard solution
Accurately pipette each 1 mL of standard reserving solution of pigment orange 5, disperse yellow 3, the each 200 μ L of all the other standard reserving solutions are in same 10 mL volumetric flasks, be settled to groove with methyl alcohol-tetrahydrofuran (volume ratio 1:1), be mixed with the mixed standard solution of 20 μ g/mL, use again the serial mixed standard solution of methyl alcohol-tetrahydrofuran (volume ratio 1:1) stepwise dilution preparation 5,2,1,0.5,0.2 μ g/mL, for the drafting of typical curve.
(4) preparation of sample solution:
Take lipstick sample approximately 0.2 g(and be accurate to 1 mg) in centrifuge tube, add tetrahydrofuran 6 mL, vortex ultrasonic 10 min, make sample dispersion and extract object, continue to add methanol-water ammonium acetate solution (step 1) approximately 4 mL in centrifuge tube, make to extract solution and be settled to 10 mL, vortex mixes rear ultrasonic 10 min, then in centrifugal 10 min of 5000 r/min.Get clarification extract, to be measured after 0.45 μ m filtering with microporous membrane.
(5) testing conditions
Liquid-phase chromatographic analysis reference conditions: chromatographic column: poroshell 120 EC-C
18(2.7 μ m, 3.0 mm × 100 mm); Column temperature: 35 DEG C; Flow velocity: 0.5 mL/min; Sample size: 2 μ L; Detect wavelength: 416 nm, 514 nm, 590 nm; Mobile phase: A 10 mmol/L ammonium acetate solutions, B acetonitrile, condition of gradient elution: in table 3
Table 3 liquid-phase chromatographic analysis condition of gradient elution
| Time, min | A，% | B，% |
| 0 | 75 | 25 |
| 3 | 62 | 38 |
| 6 | 53 | 47 |
| 9 | 20 | 80 |
| 11 | 2 | 98 |
| 14 | 2 | 98 |
| 15 | 75 | 25 |
| 18 | 75 | 25 |
(6) qualitative analysis
Respectively standard solution (step 3) and sample solution (step 4) are analyzed according to the described optimum liquid phase analysis reference conditions of step (5), the liquid chromatography separation spectrogram of the sample solution obtaining under identical liquid phase chromatogram condition is separated to spectrogram with the liquid chromatography of standard substance to be compared, in the liquid phase separation spectrogram of sample solution, there is the chromatographic peak with paratonere 53 identical retention times in discovery, the two uv absorption spectra is extremely similar, infer in this lipstick sample and may contain paratonere 53, therefore this sample is further measured through Liquid Chromatography/Mass Spectrometry, its mass spectrophotometry condition is as follows:
Liquid phase chromatogram condition: chromatographic column: poroshell 120 EC-C
18(2.7 μ m, 3.0 mm × 100 mm); Flow velocity: 0.5 μ L/min; Sample size: 2 μ L; Mobile phase: A 10 mmol/L ammonium acetate solutions, B acetonitrile-methyl alcohol (volume ratio 6:4), condition of gradient elution: 0 ~ 3 min, 40% ~ 50% B; 3 ~ 6 min, 50% ~ 85% B; 6 ~ 8 min, 85% ~ 100% B; 8 ~ 11 min, 100% ~ 100% B; 11 ~ 12 min, 100% ~ 40% B; 12 ~ 15 min, 40% ~ 40% B.
Mass spectrum reference conditions: ion gun: electron spray ionisation source (ESI source); Detection mode: multiple-reaction monitoring (MRM); Atomization gas: nitrogen, 35 Psi; Dry gas: nitrogen, flow velocity 10 L/min, temperature: 350 DEG C; Collision gas: nitrogen; Collision voltage: 380V; Capillary voltage: 4000 V; Scan pattern: negative mode; Parent ion: 375.0; Daughter ion (impact energy): 346.8(18), 204.0(24).
Confirm to find through mass spectrum, in testing result, find the extraction ion current signal of two daughter ions, determine and in this sample, really contain paratonere 53.It is proceeded to quantitative measurement.
(7) quantitative measurement
Pipette series standard solution (step 3), carry out efficient liquid phase chromatographic analysis according to chromatographic condition (step 5), taking series standard concentration of polymer solution as horizontal ordinate, peak area is ordinate, production standard curve.The peak area of the ultraviolet absorption peak with paratonere 53 under 514 nm quantitatively calculates.
The content of object in sample solution, definite by typical curve external standard method.The cubage of object in cosmetic sample.
Embodiment 4 nail oils actual samples detect
(1) preparation of salt solusion: identical with embodiment 1.
(2) preparation of standard inventory solution: identical with embodiment 1.
(3) preparation of standard solution: identical with embodiment 1.
(4) preparation of sample solution:
Take nail polish sample approximately 0.2 g(and be accurate to 1 mg) in centrifuge tube, add tetrahydrofuran 6 mL, vortex ultrasonic 10 min, make sample dispersion and extract object, continue to add methanol-water ammonium acetate solution (step 1) approximately 4 mL in centrifuge tube, make to extract solution and be settled to 10 mL, vortex mixes rear ultrasonic 10 min, then in centrifugal 10 min of 5000 r/min.Get clarification extract, to be measured after 0.45 μ m filtering with microporous membrane.
(5) testing conditions
Liquid-phase chromatographic analysis reference conditions: identical with embodiment 1.
(6) qualitative analysis
Respectively standard solution (step 3) and sample solution (step 4) are analyzed according to the described optimum liquid phase analysis reference conditions of step (5), the liquid chromatography separation spectrogram of the sample solution obtaining under identical liquid phase chromatogram condition is separated to spectrogram with the liquid chromatography of standard substance to be compared, in the liquid phase separation spectrogram of sample solution, there is the chromatographic peak with the identical retention time of solvent red 49 in discovery, the two uv absorption spectra is extremely similar, infer in this nail polish sample and may contain solvent red 49, therefore this sample is further measured through Liquid Chromatography/Mass Spectrometry, its mass spectrophotometry condition is as follows:
Liquid phase chromatogram condition: chromatographic column: poroshell 120 EC-C
18(2.7 μ m, 3.0 mm × 100 mm); Flow velocity: 0.5 μ L/min; Sample size: 2 μ L; Mobile phase: A 0.33 ‰ formic acid solution, B acetonitrile, condition of gradient elution: 0 ~ 5 min, 40% ~ 50% B; 5 ~ 6 min, 50% ~ 85% B; 6 ~ 9.5 min, 85% ~ 85% B; 9.5 ~ 9.6 min, 85% ~ 97% B; 9.6 ~ 10.5 min, 97% ~ 97% B; 10.5 ~ 11min, 97% ~ 40% B; 11 ~ 14min, 40% ~ 40% B.
Mass spectrum reference conditions: ion gun: electron spray ionisation source (ESI source); Detection mode: multiple-reaction monitoring (MRM); Atomization gas: nitrogen, 35 Psi; Dry gas: nitrogen, flow velocity 10 L/min, temperature: 350 DEG C; Collision gas: nitrogen; Collision voltage: 380V; Capillary voltage: 4000 V; Scan pattern: holotype; Parent ion: 443.2; Daughter ion (impact energy): 399.1(50), 355.0(62).
Confirm to find through mass spectrum, in testing result, find the extraction ion current signal of two daughter ions, determine and in this sample, really contain solvent red 49.It is proceeded to quantitative measurement.
(7) quantitative measurement
Pipette series standard solution (step 3), carry out efficient liquid phase chromatographic analysis according to chromatographic condition (step 5), taking series standard concentration of polymer solution as horizontal ordinate, peak area is ordinate, production standard curve.The peak area of the ultraviolet absorption peak with solvent red 49 under 514 nm quantitatively calculates.
The content of object in sample solution, definite by typical curve external standard method.The cubage of object in cosmetic sample.
。
embodiment 5loose powder class actual sample detects
(1) preparation of salt solusion: identical with embodiment 1.
(2) preparation of standard inventory solution: identical with embodiment 1.
(3) preparation of standard solution: identical with embodiment 1.
(4) preparation of sample solution:
Take eye shadow sample approximately 0.2 g(and be accurate to 1 mg) in centrifuge tube, add tetrahydrofuran 6 mL, vortex ultrasonic 10 min, make sample dispersion and extract object, continue to add methanol-water ammonium acetate solution (step 1) approximately 4 mL in centrifuge tube, make to extract solution and be settled to 10 mL, vortex mixes rear ultrasonic 10 min, then in centrifugal 10 min of 5000 r/min.Get clarification extract, to be measured after 0.45 μ m filtering with microporous membrane.
(5) testing conditions
Liquid-phase chromatographic analysis reference conditions: chromatographic column: poroshell 120 EC-C
18(2.7 μ m, 3.0 mm × 100 mm); Column temperature: 35 DEG C; Flow velocity: 0.5 mL/min; Sample size: 2 μ L; Detect wavelength: 416 nm, 514 nm, 590 nm; Mobile phase: A 10 mmol/L ammonium acetate solutions, B acetonitrile, condition of gradient elution: in table 4
Table 4: liquid-phase chromatographic analysis condition of gradient elution
| Time, min | A，% | B，% |
| 0 | 75 | 25 |
| 3 | 62 | 38 |
| 6 | 53 | 47 |
| 9 | 20 | 80 |
| 11 | 2 | 98 |
| 14 | 2 | 98 |
| 15 | 75 | 25 |
| 18 | 75 | 25 |
(6) qualitative analysis
Respectively standard solution (step 3) and sample solution (step 4) are analyzed according to the described optimum liquid phase analysis reference conditions of step (5), the liquid chromatography separation spectrogram of the sample solution obtaining under identical liquid phase chromatogram condition is separated to spectrogram with the liquid chromatography of standard substance to be compared, find the chromatographic peak of appearance and solvent red 49 and paratonere 53 identical retention times in the liquid phase separation spectrogram of sample solution, and in sample solution, the uv absorption spectra of chromatographic peak is extremely similar to standard items, infer in this eye shadow sample and may contain solvent red 49 and paratonere 53, therefore this sample is further measured through Liquid Chromatography/Mass Spectrometry, its mass spectrophotometry condition is as follows:
Liquid phase chromatogram condition: chromatographic column: poroshell 120 EC-C
18(2.7 μ m, 3.0 mm × 100 mm); Flow velocity: 0.5 μ L/min; Sample size: 2 μ L; Mobile phase: (negative mode is 10mmol/L ammonium acetate solution to A aqueous phase solution; Holotype is 0.33 ‰ formic acid solution), (negative mode is acetonitrile-methyl alcohol (volume ratio 6:4) to B organic phase solution; Holotype is acetonitrile), condition of gradient elution: in table 5
Table 5: liquid chromatography separation condition
Mass spectrum reference conditions: ion gun: electron spray ionisation source (ESI source); Detection mode: multiple-reaction monitoring (MRM); Atomization gas: nitrogen, 35 Psi; Dry gas: nitrogen, flow velocity 10 L/min, temperature: 350 DEG C; Collision gas: nitrogen; Collision voltage: 380V; Capillary voltage: 4000 V; Other mass spectrum parameters are in table 6.
The mass spectrophotometry reference parameter of 14 kinds of objects of table 6
Confirm to find through mass spectrum, in testing result, find the extraction ion current signal of corresponding daughter ion, determine and in this sample, really contain solvent red 49 and paratonere 53.It is proceeded to quantitative measurement.
(7) quantitative measurement
Pipette series standard solution (step 3), carry out efficient liquid phase chromatographic analysis according to chromatographic condition (step 5), taking series standard concentration of polymer solution as horizontal ordinate, peak area is ordinate, production standard curve.With paratonere 53 and solvent red 49, the peak area of the ultraviolet absorption peak under 514 nm quantitatively calculates.
The content of object in sample solution, definite by typical curve external standard method.The cubage of object in cosmetic sample.
。
Claims (2)
1. 14 kinds of methods that forbidding colorant detects simultaneously in cosmetics, described colorant is: acridine yellow, solvent blue 35, solvent red 49, acid violet 49, tetramethyl phosphonium chloride Pararosaniline, pigment orange 5, paratonere 53, chlorination pentamethyl Pararosaniline, Sudan II, chlorination hexamethyl Pararosaniline, SudanⅣ, rhodamine B, disperse yellow 3, S Ⅰ; It is characterized in that: detecting step is as follows:
(1) preparation of salt solusion
Ammonium acetate is joined in the mixed solution of first alcohol and water, the volume ratio of methyl alcohol and water is 1 ︰ 1, obtains methanol-water ammonium acetate solution after ammonium acetate fully dissolves, and ammonium acetate concentration is 50 ~ 250 mmol/L;
Ammonium acetate is added to the water and is fully dissolved, make the ammonium acetate solution that concentration is 10～50 mmol/L;
(2) preparation of standard solution
Equivalent takes acridine yellow respectively, solvent blue 35, solvent red 49, acid violet 49, tetramethyl phosphonium chloride Pararosaniline, pigment orange 5, paratonere 53, chlorination pentamethyl Pararosaniline, Sudan II, chlorination hexamethyl Pararosaniline, SudanⅣ, rhodamine B, disperse yellow 3, S Ⅰ is also placed in same volumetric flask, be that the methyl alcohol of 1 ︰ 1 and tetrahydrofuran solution fully dissolve and be settled to groove by volume ratio, be mixed with the mixed standard solution that each object concentration is 20 μ g/mL, be respectively 5 by methyl alcohol and a series of each object concentration of tetrahydrofuran solution stepwise dilution preparation that volume ratio is 1 ︰ 1 again, 2, 1, 0.5, the mixed standard solution of 0.2 μ g/mL, for the drafting of typical curve,
(3) preparation of sample solution:
Take cosmetic sample to be measured and be placed in centrifuge tube, in centrifuge tube, add tetrahydrofuran, the amount ratio of cosmetics to be measured and tetrahydrofuran is 0.2 g ︰ 6 mL, vortex ultrasonic 10 min, make sample dispersion or with 80 DEG C of water-baths suitable heating 1 ~ 2 min, extract object, to the methanol-water ammonium acetate solution that adds (1) step gained in centrifuge tube, the amount ratio of tetrahydrofuran and methanol-water ammonium acetate solution is 6 mL ︰ 4 mL, make to extract solution and be settled to tetrahydrofuran and methanol-water ammonium acetate solution sum, vortex mixes rear ultrasonic 10 min, then in centrifugal 10 min of 5000 r/min, get clarification extract, to be measured after 0.45 μ m filtering with microporous membrane,
(4) liquid-phase chromatographic analysis, reference conditions are as follows:
Chromatographic column: poroshell 120 EC-C
18, 2.7 μ m, 3.0 mm × 100 mm or quite person; Column temperature: 35 DEG C; Flow velocity: 0.5 mL/min; Sample size: 2 μ L; With DAD detecting device detect wavelength: 416 nm, 514 nm, 590 nm; Mobile phase: A is 10～50 mmol/L ammonium acetate solutions that (1) step makes, B acetonitrile, gradient elution;
(5) mass spectrum confirmation, reference conditions are as follows:
Liquid phase chromatogram condition: chromatographic column: poroshell 120 EC-C
18, 2.7 μ m, 3.0 mm × 100 mm or quite person; Flow velocity: 0.5 μ L/min; Sample size: 2 μ L; Mobile phase: A aqueous phase solution, negative mode is 10mmol/L ammonium acetate solution; Holotype is 0.33 ‰ formic acid solution, B organic phase solution, and negative mode is acetonitrile and methyl alcohol, the volume ratio of acetonitrile and methyl alcohol is 6 ︰ 4; Holotype is acetonitrile, gradient elution;
Mass spectrum reference conditions: ion gun: electron spray ionisation source (ESI source); Detection mode: multiple-reaction monitoring (MRM); Atomization gas: nitrogen, 35 Psi; Dry gas: nitrogen, flow velocity 10 L/min, temperature: 350 DEG C; Collision gas: nitrogen; Collision voltage: 380V; Capillary voltage: 4000 V; Other mass spectrum parameters are as follows:
The mass spectrophotometry reference parameter of object
;
(6) qualitative analysis
The sample solution that the standard solution of respectively (2) step being obtained and (3) step obtain is analyzed according to optimum liquid phase analysis reference conditions described in (4) step, the liquid chromatography separation spectrogram of the sample solution obtaining under identical liquid phase chromatogram condition is separated to spectrogram with the liquid chromatography of standard substance to be compared, if there is the chromatographic peak that retention time is consistent with the retention time of certain standard substance in sample spectrogram, and the ultraviolet absorpting spectrum after its background correction is consistent with the ultraviolet absorpting spectrum of this standard substance, can tentatively assert and in sample, have this material; Be defined as positive sample through liquid phase chromatography, must carry out mass spectrophotometry through the mass spectrum confirmation reference conditions described in (5) step and further confirm;
(7) quantitative measurement
Pipette (2) step series standard solution, carry out efficient liquid phase chromatographic analysis according to (4) step chromatographic condition, taking series standard concentration of polymer solution as horizontal ordinate, peak area is ordinate, production standard curve; Acridine yellow and disperse yellow 3 quantitatively calculate according to the uv absorption under 416 nm, paratonere 53, solvent red 49, pigment orange 5, S Ⅰ, Sudan II, SudanⅣ, alkaline purple 10 quantitatively calculate according to the uv absorption under 514 nm, and acid violet 49, tetramethyl phosphonium chloride Pararosaniline, chlorination pentamethyl Pararosaniline, chlorination hexamethyl Pararosaniline, solvent blue 35 quantitatively calculate according to the uv absorption under 590 nm;
Be the hydrochloride of solvent red 49 in view of alkaline purple 10 is real, identical with the appearance time of solvent red 49 in the method, it is alkaline purple 10 or solvent red 49 that method cannot be differentiated.
Unless 2. known, otherwise be unified test result, suggestion selective solvent red 49 is as standard substance, and test result is reported the content in solvent red 49;
The content of object in sample solution, definite by typical curve external standard method; In cosmetic sample, the content of object calculates by " formula (1) ";
In formula:
c---the mass concentration of object in the sample solution calculating from typical curve, μ g/mL;
V---press the tested sample liquid cumulative volume of extension rate conversion, mL;
M---take the quality of sample, g;
Result of calculation retains three position effective digitals;
If the mass concentration of object exceedes the upper limit of the calibration curve range of linearity in solution to be measured, after must suitably diluting liquid to be measured, redeterminate.
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