CN102393438B - Method for simultaneously determining residual quantities of sixteen sensitized aldehyde and ketone perfumes in toy - Google Patents
Method for simultaneously determining residual quantities of sixteen sensitized aldehyde and ketone perfumes in toy Download PDFInfo
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Abstract
The invention relates to a method for simultaneously determining residual quantities of sixteen sensitized aldehyde and ketone perfumes in a toy, and firstly discloses a method for simultaneously determining the residual quantities of the sixteen sensitized aldehyde and ketone perfumes consisting of 5-methyl-2,3-hexanedione, trans-2-heptenal, trans-2-hexenaldimethylacetal, citral, cinnaldehyde, hydroxycitronellal, benzalacetone, 2,4-dihydroxy-3-methylbenzaldehyde, alpha-isomethylionone, lilial, 6,10-dimethyl-3,5,9-undecatrien-2-one, 4-(4-methoxyphenyl)-3-butylene-2-one, alpha-amyl cinnamic aldehyde, lyral, 1-(4-methoxyphenyl)-1-pentene-3-one, and hexylcinnamaldehyde in the toy to fill the technological blank. The method which allows cloth toys, paster toys, and plastic toys (the ABS material, the PVC material and the PS material) to be detected has the advantages of wide coverage and strong applicability. The method which adopts the ion trap-mass spectrum in a qualitative and quantitative secondary mass spectrum MS/MS mode has a good qualitative and quantitative capability to complex matrix toy samples.
Description
Technical field
The present invention relates to a kind of detection technique, especially relate to a kind of method of simultaneously measuring 16 kinds of aldoketones sensitization aromatic residual quantities in toy.
Background technology
Often can add spices or aromatizing agent so that toy is fragrant in the production run of toy, thereby increase its attractive force for children.Essence and flavoring agent is comprised of to hundreds of organism with aromatic odor tens of usually, and these compounds are also not all safe and harmless, and some material has stronger sensitization, i.e. so-called sensitization aromatic.Correlative study shows, has at least the people of 1-2%, after the contact fragrance matter, allergic symptom can occur, the dermatitis unbearably etc. such as the breathing problems such as asthma, headache, mucosal symptoms, itch.When the toy that contains allergenic substance is played by children, these materials can enter in body by modes such as skin, suction, salivas, thereby children's health is worked the mischief.With respect to the adult, children are more responsive to chemical substance, therefore also more easily come to harm.16 kinds of aromatic that European Union will relate to herein in No. 2009/48/EC new instruction of passing through in 2009 limit the use of material in classifying toy as, and content all must not be higher than 100mg/kg.
Both at home and abroad about the research report of aromatic detection method in product, what relate to is mainly the aspects such as cosmetics, essential oil, food, room air at present.Common detection method mainly contains vapor-phase chromatography, gas-matter coupling method, high performance liquid chromatography, liquid-matter coupling method etc., and the sample pre-treatments mode is mainly Static Headspace, headspace solid-phase microextraction, vibration solvent extraction, ultrasonic secondary solvent extraction etc.And, for the study on determination method of aromatic residual quantity in toy, in domestic and foreign literature and standard, report is less.
Summary of the invention
Technical matters solved by the invention is to provide a kind of method of simultaneously measuring 16 kinds of aldoketones sensitization aromatic residual quantities in toy, it has developed the method that gas phase chromatogram-ion trap tandem mass spectrometry is measured 16 kinds of aldoketones sensitization aromatic residual quantities in toy simultaneously first, has filled up technological gap; This method can detect cotton flannel toy, paster toy, plastic toy (ABS material, PVC material, PS material) etc., and coverage rate is wider, and application is stronger; Toy sample for the matrix complexity has qualitative, quantitative ability preferably.
In order to achieve the above object, the technical solution used in the present invention is: a kind of method of simultaneously measuring 16 kinds of aldoketones sensitization aromatic residual quantities in toy, after the toy sample is carried out to pre-treatment, adopt the gas phase chromatogram-ion trap mass spectroscopy, the condition of gas phase chromatogram-ion trap mass spectroscopy is:
(1) capillary chromatographic column: HP-1 MS capillary column: 50m * 0.2mm * 0.5 μ m, or equivalent person; HP-1MS is non-polar column, is more suitable for the separation of aldoketones material;
(2) temperature programme: initial temperature is 50 ℃, keeps rising to 155 ℃ with 5 ℃/min speed after 1min, keeps 6min, then with 3 ℃/min speed, rises to 280 ℃;
(3) carrier gas: high-purity helium, flow velocity is 0.7mL/min;
(4) injector temperature is 280 ℃; The sample introduction pattern is Splitless injecting samples;
(5) analysis temperature of ion trap mass spectrometry is: 220 ℃ of ion trap temperature, vacuum subassembly temperature 50 C, 280 ℃ of transmission line temperature; The ionization mode is EI; Ionizing energy is 70eV.
Method of the present invention, wherein said aldoketones sensitization aromatic is 5-methyl-2,3-acetyl butyryl, trans-2-heptenal, trans-2-hexenoic aldehyde dimethyl-acetal, citral, cinnamic acid, laurine, benzalacetone, 2,4-dihydroxy-3-tolyl aldehyde, α-daphnone, lilial, 6,10-dimethyl-3,5,9-, 11 triolefins-2-ketone, 4-(4-anisyl)-3-butene-2-one, alpha-amyl cinnamic aldehyde, lyral, 1-(4-anisyl)-1-penten-3-one, jasminolene.
Method of the present invention, when the toy sample is cloth suede or paster type toy sample, described pretreatment process is: the toy sample is shredded to 5mm * 5mm with scissors, mix; Accurately take the 1.0g sample, be placed in container, add 20mL acetone as extracting solvent, closed container, ultrasonic extraction 20min under room temperature; Draw supernatant in extract, excessively supply after 0.45 μ m micropore PTFE filter membrane to measure.When the toy sample is the plastic toy sample, described pretreatment process is: the toy sample is pulverized or shredded with scissors with the cutting and grinding instrument, take the 1.0g sample in container, add the 10mL organic solvent dissolution, ABS plastic acetone solution wherein, the PS plastics dissolve with methylene chloride, and the PVC plastics dissolve with tetrahydrofuran; Sonic oscillation 15min; To be dissolved fully after, drip 10mL methyl alcohol, jolting is complete to the plastic matrix precipitation, solution is moved to centrifuge tube, then use 5mL washed with methanol container, then be incorporated in centrifuge tube, centrifugal 8min under 13000r/min, 4 ℃ of conditions, settled solution after centrifugal is crossed the graphitized carbon solid phase extraction column, and methanol-eluted fractions is collected all post liquid of crossing in the heart bottle; Solution is steamed to the 4mL left and right at 10kPa, 35 ℃ of condition backspins, be transferred in the nitrogen blowpipe with scale, then by proper amount of acetone, rinse the heart bottle, be incorporated in the nitrogen blowpipe, be settled to 5mL, then supply Instrument measuring after solution is crossed to 0.45 μ m micropore PTFE filter membrane.
Gas phase chromatogram-ion trap tandem mass spectrometry technology provided by the invention detects the assay method of 16 kinds of aromatic residual quantities such as lilial in toy simultaneously, than gas chromatography and single-stage mass spectrum, this method is highly sensitive, antijamming capability is strong, can be applicable to better the toy sample analysis that the matrix background interference is serious.
The method of simultaneously measuring 16 kinds of aldoketones sensitization aromatic residual quantities in toy of the present invention, develop first gas phase chromatogram-ion trap tandem mass spectrometry and measured 5-methyl-2 in toy simultaneously, the 3-acetyl butyryl, trans-2-heptenal, trans-2-hexenoic aldehyde dimethyl-acetal, citral, cinnamic acid, laurine, benzalacetone, 2, 4-dihydroxy-3-tolyl aldehyde, α-daphnone, lilial, 6, 10-dimethyl-3, 5, 9-11 triolefins-2-ketone, 4-(4-anisyl)-3-butene-2-one, alpha-amyl cinnamic aldehyde, lyral, 1-(4-anisyl)-1-penten-3-one, the method of 16 kinds of sensitization aromatic residual quantities of jasminolene, filled up technological gap, this method can detect cotton flannel toy, paster toy, plastic toy (ABS material, PVC material, PS material), and coverage rate is wider, and application is stronger.Ion trap mass spectrometry adopts second order ms MS/MS quantitative and qualitative analysis, for the toy sample of matrix more complicated, has qualitative, quantitative ability preferably; 16 kinds of materials of the existing detection wherein method of part material are to adopt GC-MS to detect mostly, and comparatively speaking, GC-MS is when making the more complicated sample of matrix, and the qualitative, quantitative ability limits to some extent.And GC-MS/MS can get rid of the matrix background interference preferably, thereby greatly increase the qualitative, quantitative ability.
Embodiment
For further illustrating the present invention, illustrate with the following Examples:
1, sample pre-treatments
Cloth suede and paster toy: the toy sample is shredded to 5mm * 5mm with scissors, mix.Accurately take 1.0g sample (being accurate to 1mg), be placed on (or in 50mL test tube with ground stopper) in the 50mL conical flask, add 20mL acetone as extracting solvent, jam-pack bottle stopper, sealed membrane sealing, ultrasonic extraction 20min under room temperature.Draw supernatant in extract, excessively measure for gas phase chromatogram-ion trap mass spectrometry after 0.45 μ m micropore PTFE filter membrane.
Plastic toy: the toy sample is pulverized or shredded with scissors with the cutting and grinding instrument, take the 1.0g sample in the 50mL conical flask, add the 10mL agent dissolves (the ABS plastic acetone solution, the PS plastics dissolve with methylene chloride, the PVC plastics dissolve with tetrahydrofuran), sonic oscillation 15min.To be dissolved fully after, drip 10mL methyl alcohol, jolting, until the plastic matrix precipitation fully, moves to centrifuge tube by solution, then uses 5mL washed with methanol conical flask, then is incorporated in centrifuge tube, centrifugal 8min under 13000r/min, 4 ℃ of conditions, get settled solution stand-by.
With 5mL methyl alcohol rinse Envi-carb graphitized carbon solid phase extraction column, the settled solution after centrifugal is crossed to post, the 10mL methanol-eluted fractions, collect all post liquid of crossing in the heart bottle.Solution is steamed to the 4mL left and right at 10kPa, 35 ℃ of condition backspins, be transferred in the nitrogen blowpipe with scale, then by proper amount of acetone, rinse the heart bottle, be incorporated in the nitrogen blowpipe, be settled to 5mL (more than 5mL, available slow nitrogen stream blows to being less than 5mL, is settled to 5mL and gets final product as solution).After being crossed to 0.45 μ m micropore PTFE filter membrane, solution supplies Instrument measuring.
Discussion in pre-treatment step:
A. plastic sample pre-treating method commonly used has accelerated solvent extraction, Solid-Phase Extraction, ultrasonic extraction, microwave abstracting etc.This method is taked ultrasonic supplementary mode, utilizes suitable organic solvent that plastics are fully dissolved, and then with methyl alcohol, as precipitation agent, makes the plastic matrix precipitation, thereby organism residual in plastics can be extracted more fully.Method has compared the solute effect of methyl alcohol, acetone, methylene chloride, normal hexane, toluene, ethyl acetate, tetrahydrofuran, DMF, found that the ABS plastic acetone solution, and the PS plastics dissolve with methylene chloride, and the PVC plastics dissolve with tetrahydrofuran, and effect is better.Adopt methyl alcohol as precipitation agent, can effectively make the plastics precipitation.Plastic toy matrix more complicated, the effect of Solid-Phase Extraction is mainly pigment and some other impurity of removing in matrix.The graphitized carbon solid phase extraction column is better to the adsorption effect of pigment, uses the 10ml methanol-eluted fractions, and the wash-out object can be retained in the impurity such as pigment on post again fully.
B. cloth suede and paster toy sample adopt ultrasonic extracting mode to be extracted, and after extracting, solution needs filtering membrane to remove small particle.In actual the detection, find, in most cases the solution after acetone extraction cloth suede or paster toy sample is without color or very slight color, now directly after filtering membrane, go up machine mensuration, if solution colour is darker, can, with reference to the disposal route of plastic toy sample, with methyl alcohol, solution be settled to the 25mL left and right, Solid-Phase Extraction and to revolve the steaming condition constant, finally be settled to 5mL, measure through machine on filter membrane, result also can meet the demands.
2, gas phase chromatogram-ion trap mass spectroscopy condition
Gas chromatography is separated to the actual conditions adopted, comprise that chromatographic column kind, temperature programme condition, sample introduction pattern etc. are not construed as limiting, the every method that can effectively separate 16 kinds of target substances all can be used.
What below provide is typical condition determination.
A. instrument configuration: Varian 450-240 gas phase chromatogram-ion trap mass spectrometer (GC-IT-MS/MS)
B. capillary chromatographic column: HP-1MS capillary column (brand: Agilent Agilent): 50m * 0.2mm * 0.5 μ m, or equivalent person;
C. temperature programme: initial temperature is 50 ℃, keeps rising to 155 ℃ with 5 ℃/min speed after 1min, keeps 6min, then with 3 ℃/min speed, rises to 280 ℃;
D. carrier gas: high-purity helium, flow velocity is 0.7mL/min;
E. injector temperature: 280 ℃; Sample introduction pattern: Splitless injecting samples;
F. detecting device: ion trap mass spectrometry (IT-MS/MS);
G. analysis temperature: 220 ℃ of ion trap temperature (Trap Temperature), 50 ℃ of vacuum subassembly temperature (Manifold Temperature), 280 ℃ of transmission line temperature (Transfer Line Temperature);
H. ionization mode: EI; Ionizing energy: 70eV;
I. monitoring mode: MS/MS;
J. crash mode: resonance mode;
K. control (Target TIC) from gain: 20000;
L. filament current (Emission Current): 10 uAmps;
M. solvent delay 5min.
The essential information of 16 kinds of target substances, chromatographic retention and mass spectrophotometry parameter are specifically in Table 1.
The chromatogram of 16 kinds of materials of table 1 and mass spectrophotometry parameter
Annotate: with the first-selected quota ion of the conduct of *
3, the preparation of standard solution and standard working curve
Take the standard items 0.05g (being accurate to 0.1mg) of each material to the brown volumetric flask of 100ml, the acetone constant volume, obtaining respectively concentration is each material list mark and the complete mixed standard inventory solution of 500mg/L, is placed in 4 ℃ and keeps in Dark Place.During use, draw as required appropriate standard inventory solution, the working solution by acetone diluted to respective concentration, concentration range is 0.01mg/L～50mg/L.
Under the chromatographic condition of setting, standard operation solution to be measured from low to high successively by concentration, the peak area of the quota ion chromatographic peak that obtains of take is ordinate, the sample introduction concentration of each corresponding material is the horizontal ordinate mapping, the drawing standard working curve.Result shows, 2,4-dihydroxy-3-tolyl aldehyde linearity is slightly poor, and related coefficient is 0.9768, and all the other each materials are in its range of linearity, and concentration value and peak area have good linear relationship, and linearly dependent coefficient all is greater than 0.9968.
This method using response signal while being greater than 10 times of noises corresponding content of material as quantitative limit, when measuring cloth suede and paster sample, determine that the quantitative limit of each material all is less than 10mg/kg, when measuring plastic sample, the quantitative limit of each material all is less than 2.5mg/kg.Detailed results is as shown in table 2.
The quantitative limit of the range of linearity of 16 kinds of materials of table 2, related coefficient, method
4, the recovery of method and precision
We have set 3 for every kind of material and have added concentration, by the determined experiment condition of this method, each is added to concentration and repeat 6 tests.For plastic sample, on the employing toy market, modal ABS plastic toy is as blank matrix.From result, method is for the recovery of different material between 81.2%-110.4%, and relative standard deviation (RSD) is between 1.2%-9.8%.Concrete data are in Table 3.
The recovery of table 3 method and precision (n=6)
5, the mensuration of toy actual sample
Application this method, to stochastic buying from the market to 5 kinds of cotton flannel toies, 5 kinds of paster toys and 5 kinds of plastic toys mensuration of carrying out above-mentioned 16 kinds of sensitization aromatic residual quantities.Measurement result is, in 3 kinds of paster toys, detects laurine, and content is respectively 22.4mg/kg, 14.5mg/kg and 11.5mg/kg; Detect benzalacetone in 3 kinds of paster toys, content is respectively 19.5mg/kg, 18.8mg/kg and 11.0mg/kg; Detect 6,10-dimethyl-3,5 in a kind of paster toy, 9-11 triolefins-2-ketone, content is 99.8mg/kg; Detect benzalacetone in 2 kinds of plastic toys, content is respectively 1.7mg/kg and 4.6mg/kg; Detect α-daphnone in a kind of plastic toy, content is 4.2mg/kg.All the other all do not detect.
Above-described embodiment is described the preferred embodiment of the present invention; not scope of the present invention is limited; design under the prerequisite of spirit not breaking away from the present invention; various distortion and improvement that the common engineering technical personnel in this area make technical scheme of the present invention, all should fall in the definite protection domain of claims of the present invention.
Claims (3)
1. a method of simultaneously measuring 16 kinds of aldoketones sensitization aromatic residual quantities in toy is characterized in that: after the toy sample is carried out to pre-treatment, adopt the gas phase chromatogram-ion trap mass spectroscopy, the condition of gas phase chromatogram-ion trap mass spectroscopy is:
(1) capillary chromatographic column: HP-1MS capillary column;
(2) temperature programme: initial temperature is 50 ℃, keeps rising to 155 ℃ with 5 ℃/min speed after 1min, keeps 6min, then with 3 ℃/min speed, rises to 280 ℃;
(3) carrier gas: high-purity helium, flow velocity is 0.7mL/min;
(4) injector temperature is 280 ℃; The sample introduction pattern is Splitless injecting samples;
(5) analysis temperature of ion trap mass spectrometry is: 220 ℃ of ion trap temperature, vacuum subassembly temperature 50 C, 280 ℃ of transmission line temperature; The ionization mode is EI; Ionizing energy is 70eV;
Described 16 kinds of aldoketones sensitization aromatic are 5-methyl-2,3-acetyl butyryl, trans-2-heptenal, trans-2-hexenoic aldehyde dimethyl-acetal, citral, cinnamic acid, laurine, benzalacetone, 2,4-dihydroxy-3-tolyl aldehyde, α-daphnone, lilial, 6,10-dimethyl-3,5,9-, 11 triolefins-2-ketone, 4-(4-anisyl)-3-butene-2-one, alpha-amyl cinnamic aldehyde, lyral, 1-(4-anisyl)-1-penten-3-one, jasminolene.
2. method according to claim 1, it is characterized in that: when the toy sample is cloth suede or paster type toy sample, described pretreatment process is: the toy sample is shredded to 5mm * 5mm with scissors, mix; Accurately take the 1.0g sample, be placed in container, add 20mL acetone as extracting solvent, closed container, ultrasonic extraction 20min under room temperature; Draw supernatant in extract, excessively supply after 0.45 μ m micropore PTFE filter membrane to measure.
3. method according to claim 1, it is characterized in that: when the toy sample is the plastic toy sample, described pretreatment process is: the toy sample is pulverized or shredded with scissors with the cutting and grinding instrument, take the 1.0g sample in container, add the 10mL organic solvent dissolution, ABS plastic acetone solution wherein, the PS plastics dissolve with methylene chloride, and the PVC plastics dissolve with tetrahydrofuran; Sonic oscillation 15min; To be dissolved fully after, drip 10mL methyl alcohol, jolting is complete to the plastic matrix precipitation, solution is moved to centrifuge tube, then use 5mL washed with methanol container, then be incorporated in centrifuge tube, centrifugal 8min under 13000r/min, 4 ℃ of conditions, settled solution after centrifugal is crossed the graphitized carbon solid phase extraction column, and methanol-eluted fractions is collected all post liquid of crossing in the heart bottle; Solution is steamed to 4mL at 10kPa, 35 ℃ of condition backspins, be transferred in the nitrogen blowpipe with scale, then by proper amount of acetone, rinse the heart bottle, be incorporated in the nitrogen blowpipe, be settled to 5mL, then supply Instrument measuring after solution is crossed to 0.45 μ m micropore PTFE filter membrane.
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| CN106370755A (en) * | 2016-11-14 | 2017-02-01 | 山东出入境检验检疫局检验检疫技术中心 | Method for measuring content of sensitization aromatizer in aromatic pen |
| CN106770706A (en) * | 2016-11-14 | 2017-05-31 | 山东出入境检验检疫局检验检疫技术中心 | The assay method of sensitization fragrance level in a kind of plastic material |
| CN106959344A (en) * | 2016-11-14 | 2017-07-18 | 山东出入境检验检疫局检验检疫技术中心 | The assay method of sensitization fragrance level and volatile quantity in a kind of textile material |
| CN106990174B (en) * | 2017-02-21 | 2019-07-09 | 中国检验检疫科学研究院 | SVOC rapid detection method in a kind of cloth velvet sample based on full volatilization head space |
| CN106770800B (en) * | 2017-02-21 | 2019-04-16 | 中国检验检疫科学研究院 | The rapid detection method of 58 kinds of sensitization aromatic in a kind of articles for children |
| CN108828102B (en) * | 2018-08-20 | 2020-11-03 | 云南同创检测技术股份有限公司 | Method for determining content of pineapple ester and jasmal in essence and flavor |
| CN109541083B (en) * | 2019-01-30 | 2022-05-10 | 广州质量监督检测研究院 | Method for detecting volatile odor substances in polyvinyl chloride product |
| CN110702920B (en) * | 2019-10-14 | 2022-12-09 | 深圳市药品检验研究院（深圳市医疗器械检测中心） | Method for detecting sensitization of cosmetics containing cinnamaldehyde |
| CN112098543B (en) * | 2020-08-31 | 2022-07-22 | 深圳天祥质量技术服务有限公司 | Method for measuring contents of various perfume compounds in sole material |
| CN112034072B (en) * | 2020-09-12 | 2023-05-12 | 河南牧业经济学院 | Method for measuring content and condensation degree of citral diethyl acetal and laural diethyl acetal in perfume by gas chromatography-tandem mass spectrometry |
| CN114034848A (en) * | 2021-11-23 | 2022-02-11 | 通标标准技术服务有限公司 | Method for measuring allergic aromatic in plastic toy |
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