CN104634889B - On-chip derivatization measures the method for Formaldehyde In Cosmetics - Google Patents
On-chip derivatization measures the method for Formaldehyde In Cosmetics Download PDFInfo
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Abstract
The present invention relates to the assay method of a kind of On-chip derivatization-liquid chromatography for measuring Formaldehyde In Cosmetics, step is as follows: 1) extract: weigh sample, is placed in tool plug graduated centrifuge tube, adds appropriate acetonitrile, and vortex dissolves；Using acetonitrile constant volume, after covering plug, vortex mixes；Cross microporous filter membrane, measure for HPLC in filtrate 2h；2) preparation of formaldehyde standard working solution；3) measure: according to the standard working solution series that the selected peak area of the situation of concentration of formaldehyde in sample liquid is close, standard working solution and sample liquid equal-volume ginseng inject sample and measure, qualitative by retention time, quantified by external standard method；4) blank assay: except being not added with sample, by above-mentioned 1) and 3) operating procedure carries out；5) result calculates and statement: calculating the residual quantity of formaldehyde in sample by formula or adopt Chromatographic data system to calculate, result of calculation need to deduct blank value.This invention simplifies sample preparation steps, improve detection efficiency, quickly, easy, repeatability is high.
Description
Technical field
The present invention relates to the assay method of a kind of On-chip derivatization-liquid chromatography for measuring Formaldehyde In Cosmetics.
Background technology
Formaldehyde is commonly called as formalin, be colourless, there is the irritative gas of overpowering odor, its aqueous solution of 35%～40% common name formalin.Formaldehyde is confirmed as carcinogenic and teratogen by World Health Organization (WHO), controls to be in second on list at China's toxic chemical.In January, 2011, the quick early warning system of European Union's non-food stuff consumer product has circulated a notice of the free formaldehyde content excessive problem in the defeated europeanized cosmetic of China.Limitation in the cosmetics instruction 76/768/EEC of comparison European Union, the three batches of hair conditioner Free-formaldehyde content being notified have exceeded 8 times more than of Limited Doses, will be returned goods or even destroy.In November, 2011, safety of America cosmetics sports league announces, part Johnson & Johnson baby shampoo contain can be carcinogenic dioxanes and discharge quaternary ammonium salt-15 of trace formaldehyde, and call consumer boycott Johnson & Johnson baby shampoo, until these products are no longer containing harmful chemical.Formaldehyde In Cosmetics excessive problem increasingly causes the concern of consumer.
Containing formaldehyde and the sterilization antiseptic of releasable formaldehyde in cosmetics, formaldehyde slow releasing agent is generally added in cosmetics, reaches sterilization and anticorrosion purpose by slow releasing formaldehyde or derivant.China's " cosmetics health specification " (2007 editions) regulation formaldehyde is regulated substance, dental health product≤0.1%, other product≤0.2% (all in free formaldehyde), and scleronychia agent≤5% is forbidden for spray product simultaneously.When in finished product, formaldehyde mass fraction is more than 0.05% (in free formaldehyde), it is necessary to head-stamp on Product labelling " containing formaldehyde ".The formaldehyde slow releasing agent class preservative that in cosmetics, utilization rate is higher mainly has: the bromo-2-nitro-1 of 2-, ammediol, Bis(hydroxymethyl)imidazolidinyl urea, imidazolidinyl urea, DMDM Hydantoin, quaternary ammonium salt-15, hexamethylenamine, paraformaldehyde etc., up to tens kinds, " cosmetics health specification " (2007 editions) specify that its limitation is not 0.1%～0.6% not etc..
Certain seminar external analyzes emollient cream of Sweden, and result show in the sample of 10% containing formaldehyde (0.02%～0.09%), though these products are not directly added into formaldehyde, but mostly contains the preservative of releasable formaldehyde.Domestic market has the hexamethylenamine that many deodorization or antiperspirant class cosmetics contain up to 20%～40% concentration, it is possible to the health of consumer is constituted a threat to.Bibliographical information formaldehyde cause allergy or dermatitis needed for threshold concentration very low, respectively 30 μ g/L (0.003%) and 250 μ g/L (0.0025%).
European Union's cosmetic chemistry is analyzed method working group and is found when developing the analysis method of formaldehyde slow releasing agent class preservative, and these materials quickly discharge formaldehyde when being dissolved in water and other polar solvent.The number of formaldehyde donor release formaldehyde amount is relevant with the physicochemical environment residing for Form aldehyde release body, increases with pH value, the increase of temperature and time.The assay method of Formaldehyde In Cosmetics mainly has colorimetry, column front derivation-chromatography, post-column derivation method and nuclear magnetic resonance method.The difficult point of Formaldehyde In Cosmetics detection is that, in sample pretreatment process, formaldehyde slow releasing agent decomposes in a large number and causes that formaldehyde examination result is higher.Colorimetry can measure formaldehyde total amount, and in derivatization process, formaldehyde slow releasing agent decomposes, and detection formaldehyde is free formaldehyde, composite formaldehyde and polymerization formaldehyde total amount.Post-column derivation method can measure free formaldehyde, free formaldehyde and formaldehyde slow releasing agent are separated by liquid chromatograph, post-column derivation avoids the interference of formaldehyde slow releasing agent, but at sample extraction and purification process, formaldehyde slow releasing agent can discharge formaldehyde when being dissolved in water or other polar solvent.Column front derivation-chromatography, adopts derivatization reaction-extraction blocked method, can effectively suppress formaldehyde slow releasing agent to decompose release formaldehyde, but manual operation is consuming time, and repeatability is not good.Nuclear magnetic resonance method is as a kind of pure physical method, though without influence on the balance between free formaldehyde and formaldehyde slow releasing agent, but nuclear magnetic resonance apparatus is expensive, and method is difficult to promote.
Summary of the invention
In order to solve the technological deficiency existed in the assay method of above-mentioned Formaldehyde In Cosmetics, the method that it is an object of the invention to provide a kind of On-chip derivatization-liquid chromatography for measuring Formaldehyde In Cosmetics, the method adopts formaldehyde in acetonitrile extraction sample, 2, the acetonitrile of 4-dinitrophenylhydrazine-acetic acid (4:1, v/v) solution is derivative liquid, on-line automatic derivative, liquid chromatography for measuring.
In order to realize above-mentioned purpose, present invention employs following technical scheme:
On-chip derivatization measures the method for Formaldehyde In Cosmetics, and the method comprises the following steps:
1) extract
Weighing sample 0.2g, be accurate to 0.001g, be placed in 10mL tool plug graduated centrifuge tube, add appropriate acetonitrile, vortex dissolves；Being settled to 10mL with acetonitrile, after covering plug, vortex mixes 1min, the centrifugal 3min of speed to be not less than 3000r/min；Cross microporous filter membrane, measure for HPLC in filtrate 2h；
2) preparation of formaldehyde standard working solution
Pipetting appropriate formaldehyde Standard Stock solutions, be placed in 10mL volumetric flask, be settled to 10mL with acetonitrile, after covering plug, vortex mixes, and measures for HPLC；The concentration of above-mentioned formaldehyde Standard Stock solutions is 100mg/L；
3) measure
According to the standard working solution series that the selected peak area of the situation of concentration of formaldehyde in sample liquid is close, in standard working solution and sample liquid, the response value of formaldehyde derivatives all should in the range of linearity of instrument detection, standard working solution and sample liquid equal-volume ginseng inject sample and measure, qualitative by retention time, quantified by external standard method；Liquid phase chromatogram condition is:
A) chromatographic column: C18Post, 150mm × 4.6mm internal diameter, 5 μm, or suitable person；
B) mobile phase: acetonitrile-water, volume ratio is 65:35；
C) flow velocity: 1.0mL/min；
D) detection wavelength: 355nm；
E) automatic derivatization program: draw derivative liquid 10 μ L, sample solution 5 μ L, derivative liquid 10 μ L, be sufficiently mixed, react 2min, sample introduction；The mixed solution that the above-mentioned acetonitrile solution that derivative liquid is 2,4 dinitrophenyl hydrazine is constituted with acetic acid, the concentration of 2,4 dinitrophenyl hydrazine is 2g/L, acetonitrile in derivative liquid: the volume ratio of acetic acid is 4:1；
4) blank assay
Except being not added with sample, by above-mentioned 1) and 3) operating procedure carries out；
5) result calculates and statement
Calculating the residual quantity of formaldehyde in sample as follows or adopt Chromatographic data system to calculate, result of calculation need to deduct blank value:
In formula:
The residual quantity of formaldehyde in X sample, unit is μ g/g；
The peak area of formaldehyde derivatives in A sample liquid；
The concentration of formaldehyde derivatives in c standard solution, unit is mg/L；
The final constant volume of V sample liquid, unit is mL；
The peak area of formaldehyde derivatives in As standard solution；
Sample mass representated by m sample solution, unit is g.
The present invention adopts acetonitrile extraction Formaldehyde In Cosmetics, and acetonitrile-acetic acid (4:1, the v/v) solution of 2,4 dinitrophenyl hydrazine is derivative liquid, On-chip derivatization-liquid chromatography for measuring.This invention simplifies sample preparation steps, effectively inhibit the decomposition of formaldehyde slow releasing agent, shorten analysis time, improve detection efficiency, quickly, easy, repeatability is high, is suitable for the quick mensuration of batch samples Free-formaldehyde content.
Accompanying drawing explanation
Fig. 1 is the peak area variation diagram with the derivative time of formaldehyde derivatives.
Fig. 2 is the chromatogram of concentration 1.0 μ g/mL formaldehyde standard derivative solution.
Fig. 3 is handwashing liquid blank sample chromatogram.
Fig. 4 is the sample chromatogram figure after adding formaldehyde standard specimen.
Detailed description of the invention
The following specific embodiments of the present invention is to make a detailed explanation.
1.1 method summaries
Formaldehyde in acetonitrile extraction sample.On-line automatic derivative after, at 355nm wavelength place liquid chromatogram measuring, quantified by external standard method.1.2 instruments and reagent
High performance liquid chromatograph (is furnished with diode array detector or UV-detector), high speed centrifuge, vortex instrument.Formaldehyde Standard Stock solutions (100mg/L), 2,4 dinitrophenyl hydrazine (DNPH), acetonitrile, methanol, oxolane, acetone are chromatographically pure.Unless otherwise indicated, agents useful for same is analytical pure, and water used is ultra-pure water.
1.3 determination steps
1.3.1 extract
Weighing sample 0.2g, be accurate to 0.001g, be placed in 10mL tool plug graduated centrifuge tube, add appropriate acetonitrile, vortex dissolves；Being settled to 10mL with acetonitrile, after covering plug, vortex mixes 1min, the centrifugal 3min of speed to be not less than 3000r/min；Crossing microporous filter membrane, filtrate measures for HPLC.
1.3.2 the preparation of formaldehyde standard working solution
Pipetting appropriate formaldehyde Standard Stock solutions, be placed in 10mL volumetric flask, be settled to 10mL with acetonitrile, after covering plug, vortex mixes, and measures for HPLC；
1.3.3 measure
1.3.3.1 liquid phase chromatogram condition
Liquid phase chromatogram condition is:
A) chromatographic column: C18Post, 150mm × 4.6mm (internal diameter), 3.5 μm, or suitable person；
B) mobile phase: acetonitrile-water (65+35, V+V)；
C) flow velocity: 1.0mL/min；
D) detection wavelength: 355nm；
E) automatic derivatization program: draw derivative liquid 10 μ L, sample solution 5 μ L, derivative liquid 10 μ L, be sufficiently mixed, react 2min, sample introduction.
1.3.3.2 chromatographic determination
According to the standard working solution series that the selected peak area of the situation of concentration of formaldehyde in sample liquid is close.In standard working solution and sample liquid, the response value of formaldehyde derivatives all should in the range of linearity of instrument detection.Standard working solution and sample liquid equal-volume ginseng inject sample and measure.Qualitative by retention time, quantified by external standard method.Under above-mentioned chromatographic condition, the retention time of formaldehyde derivatives is about 3min.1.3.4 blank assay
Except being not added with sample, undertaken by above-mentioned 1.3.1 and 1.3.3 operating procedure.
1.4 results calculate and statement
Calculating the residual quantity of formaldehyde in sample as follows or adopt Chromatographic data system to calculate, result of calculation need to deduct sky
White value:
In formula:
The residual quantity of formaldehyde in X sample, unit is μ g/g；
The peak area of formaldehyde derivatives in A sample liquid；
The concentration of formaldehyde derivatives in c standard solution, unit is mg/L；
The final constant volume of V sample liquid, unit is mL；
AsThe peak area of formaldehyde derivatives in standard solution；
Sample mass representated by m sample solution, unit is g.
The selection of 2.1 derivatization reaction conditions
It is respectively adopted acetonitrile-phosphate buffer (pH2) (1:1, v/v) and DNPH solution prepared by acetonitrile-acetic acid (5:1, v/v), formaldehydogenic derivative similar efficiency of spreading out under both room temperatures.Take 10mg/L formaldehyde standard solution, adopt above two DNPH solution, be respectively adopted derivative and automatic derivatization program, the peak area of formaldehyde derivatives and derivative time the curve of off-line and see Fig. 1.Adopting acetonitrile-acetic acid (4:1, v/v) to prepare DNPH solution, On-chip derivatization reaction 2min, formaldehyde-derived is complete, and derivative efficiency has reached 90% that off-line is derivative.
The selection of 2.2 Extraction solvent
Select utilization rate is higher in cosmetics Bis(hydroxymethyl)imidazolidinyl urea, imidazolidinyl urea, 1,3-dihydroxymethyl-5,5-dimethyl hydantion (DMDM Hydantoin), quaternary ammonium salt-15,5 kinds of formaldehyde slow releasing agents of hexamethylenamine, the impact of test Extraction solvent PARA FORMALDEHYDE PRILLS(91,95) slow releasing agent release formaldehyde amount.
Formaldehyde donor release formaldehyde amount number relevant with the physics residing for Form aldehyde release body and chemical environment, the formaldehyde amount discharged along with the increase of pH value, temperature and time increases.Weighing 5 kinds of formaldehyde slow releasing agent 10mg respectively, be separately added into 1mL methanol, acetonitrile, oxolane, acetone, pH2 buffer, pH7 water, pH9 buffer, vortex 1min, room temperature stands 5min, takes appropriate solution On-chip derivatization, detects releasable for maldehyde content.It is shown that methanol and aqueous solution promote formaldehyde donor alcoholysis and hydrolysis, release formaldehyde amount is higher；Acetonitrile, oxolane and acetone can better suppress formaldehyde donor to decompose.Acetone is volatile and reacts with derivating agent with formaldehyde competition.Selection acetonitrile is Extraction solvent, On-chip derivatization formaldehyde, can be prevented effectively from formaldehyde slow releasing agent and decompose.The selection of 2.3 extraction times
When test acetonitrile is Extraction solvent, extraction time increases the impact of PARA FORMALDEHYDE PRILLS(91,95) slow releasing agent release formaldehyde amount.Weighing 8 kinds of formaldehyde slow releasing agent 10mg respectively, add 1mL acetonitrile, vortex 1min, room temperature stands 5min, 1h, 2h, 24h, takes appropriate solution On-chip derivatization, detects releasable for maldehyde content.It is shown that when room temperature stands 5min, in solution, burst size of methanal is as follows: DMDM Hydantoin > quaternary ammonium salt-15 > Bis(hydroxymethyl)imidazolidinyl urea > imidazolidinyl urea > hexamethylenamine.When standing 2h, 5 kinds of formaldehyde slow releasing agent release formaldehyde total amounts are incremented by 7% than when standing 5min；When standing 24h, 5 kinds of formaldehyde slow releasing agent release formaldehyde total amounts are incremented by 55% than when standing 5min.Therefore select acetonitrile extraction liquid, in 2h, carry out HPLC mensuration.
2.4 calibration traces, detection limit and the response rate
Under the determined experiment condition of method, the mass concentration (X) of formaldehyde standard solution presents good linear relationship with its peak area (Y) within the scope of 1.0～10.0mg/L, and the calibration trace obtained is Y=218X+8.21, r2=0.9999.Select handwashing liquid blank sample, add the formaldehyde of 50,100,200 g/g3 concentration levels of μ respectively, parallel assay 6 times, the response rate of formaldehyde is 83.0%～98.4%, relative standard deviation (RSD)<5.0%, the quantitative limit of method (with signal to noise ratio (S/N)>10) for 50 μ g/g.Fig. 2 is the chromatogram of concentration 1.0 μ g/mL formaldehyde standard derivative solution, and Fig. 3 is handwashing liquid blank sample and Fig. 4 is the sample chromatogram figure after adding formaldehyde standard specimen.
Claims (1)
1. the method that On-chip derivatization measures Formaldehyde In Cosmetics, it is characterised in that the method comprises the following steps:
1) extract
Weighing sample 0.2g, be accurate to 0.001g, be placed in 10mL tool plug graduated centrifuge tube, add appropriate acetonitrile, vortex dissolves；Being settled to 10mL with acetonitrile, after covering plug, vortex mixes 1min, the centrifugal 3min of speed to be not less than 3000r/min；Cross microporous filter membrane, measure for HPLC in filtrate 2h；
2) preparation of formaldehyde standard working solution
Pipetting appropriate formaldehyde Standard Stock solutions, be placed in 10mL volumetric flask, be settled to 10mL with acetonitrile, after covering plug, vortex mixes, and measures for HPLC；The concentration of above-mentioned formaldehyde Standard Stock solutions is 100mg/L；
3) measure
According to the standard working solution series that the selected peak area of the situation of concentration of formaldehyde in sample liquid is close, in standard working solution and sample liquid, the response value of formaldehyde derivatives all should in the range of linearity of instrument detection, standard working solution and sample liquid equal-volume ginseng inject sample and measure, qualitative by retention time, quantified by external standard method；Liquid phase chromatogram condition is:
A) chromatographic column: C18Post, 150mm × 4.6mm internal diameter, 5 μm, or suitable person；
B) mobile phase: acetonitrile-water, volume ratio is 65:35；
C) flow velocity: 1.0mL/min；
D) detection wavelength: 355nm；
E) automatic derivatization program: draw derivative liquid 10 μ L, sample solution 5 μ L, derivative liquid 10 μ L, be sufficiently mixed, react 2min, sample introduction；The mixed solution that the above-mentioned acetonitrile solution that derivative liquid is 2,4 dinitrophenyl hydrazine is constituted with acetic acid, the concentration of 2,4 dinitrophenyl hydrazine is 2g/L, acetonitrile in derivative liquid: the volume ratio of acetic acid is 4:1；
4) blank assay
Except being not added with sample, by above-mentioned 1) and 3) operating procedure carries out；
5) result calculates and statement
Calculating the residual quantity of formaldehyde in sample as follows or adopt Chromatographic data system to calculate, result of calculation need to deduct blank value:
In formula:
The residual quantity of formaldehyde in X sample, unit is μ g/g；
The peak area of formaldehyde derivatives in A sample liquid；
The concentration of formaldehyde derivatives in c standard solution, unit is mg/L；
The final constant volume of V sample liquid, unit is mL；
AsThe peak area of formaldehyde derivatives in standard solution；
Sample mass representated by m sample solution, unit is g.
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| CN109342620A (en) * | 2018-11-22 | 2019-02-15 | 浙江省检验检疫科学技术研究院 | The method of means of derivation extraction Rapid Determination of Formaldehyde in Food |
| CN110231422A (en) * | 2019-07-02 | 2019-09-13 | 中山永恒检测科技有限公司 | A kind of method of online column front derivation liquid chromatogram test formaldehyde |
| CN111693632A (en) * | 2020-07-24 | 2020-09-22 | 上海市食品药品检验所 | Method for extracting total formaldehyde in cosmetics and rapid detection method |
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