CN102393438A - 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
- Publication number
- CN102393438A CN102393438A CN2011103558694A CN201110355869A CN102393438A CN 102393438 A CN102393438 A CN 102393438A CN 2011103558694 A CN2011103558694 A CN 2011103558694A CN 201110355869 A CN201110355869 A CN 201110355869A CN 102393438 A CN102393438 A CN 102393438A
- Authority
- CN
- China
- Prior art keywords
- toy
- sample
- temperature
- aldehyde
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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 measuring 16 kinds of aldoketones sensitization aromatic residual quantities in the toy simultaneously.
Background technology
Regular meeting adds spices or aromatizing agent so that toy is fragrant in the production run of toy, thereby increases its attractive force for children.Essence and flavoring agent is made up of to hundreds of organism with aromatic odor tens of usually, and these compounds not all are safe and harmless also, and some material has stronger sensitization, promptly so-called sensitization aromatic.Correlative study shows, has at least the people of 1-2% behind the contact fragrance matter, allergic symptom can take place, for example breathing problem, headache, mucosal symptoms, itch dermatitis unbearably such as asthma etc.When the toy that contains allergenic substance was played by children, these materials can get in the body through modes such as skin, suction, salivas, thereby children's health is worked the mischief.Children are more responsive to chemical substance with respect to the adult, therefore also come to harm more easily.16 kinds of aromatic that European Union relates in this paper in 2009/48/EC number that passed through in 2009 new instruction are classified as and are limited the use of material in the toy, and content all must not be higher than 100mg/kg.
Both at home and abroad about the research report of aromatic detection method in the product, what relate to mainly is 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 head space, headspace solid-phase microextraction, vibration solvent extraction, ultrasonic secondary solvent extraction etc.And for the study on determination method of aromatic residual quantity in the toy, report is less in domestic and foreign literature and the standard.
Summary of the invention
The technical matters that the present invention solved provides a kind of method of measuring 16 kinds of aldoketones sensitization aromatic residual quantities in the toy simultaneously; 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 the 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; The toy sample complicated to matrix has qualitative, quantitative ability preferably.
In order to achieve the above object; The technical scheme that the present invention adopts is: a kind of method of measuring 16 kinds of aldoketones sensitization aromatic residual quantities in the toy simultaneously; After the toy sample carried out 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 equivalents; HP-1MS is a 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 behind the 1min, keeps 6min, rises to 280 ℃ with 3 ℃/min speed then;
(3) carrier gas: high-purity helium, flow velocity are 0.7mL/min;
(4) injector temperature is 280 ℃; The sample introduction pattern is split sampling not;
(5) analysis temperature of ion trap mass spectrometry is: 220 ℃ of ion trap temperature, 50 ℃ of vacuum subassembly temperature, 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-the 2-heptenal, anti--2-hexenoic aldehyde dimethyl-acetal, citral, cinnamic acid, laurine, benzalacetone, 2; 4-dihydroxy-3-tolyl aldehyde, α-Yi Jiajiziluolantong, lilial, 6; 10-dimethyl-3,5,9-11 triolefins-2-ketone, 4-(4-anisyl)-3-butene-2-ketone, alpha-amyl cinnamic aldehyde, lyral, 1-(4-anisyl)-1-penten-3-one, jasminolene.
Method of the present invention, when the toy sample was cloth suede or paster type toy sample, said pre-treatment process was: the toy sample is shredded to 5mm * 5mm mixing with scissors; Accurately take by weighing the 1.0g sample, be placed in the container, add 20mL acetone as extracting solvent, closed container, ultrasonic Extraction 20min under the room temperature; Draw supernatant in the extract, supply behind the 0.45 μ m micropore PTFE filter membrane excessively to measure.When the toy sample is the plastic toy sample; Said pre-treatment process is: the toy sample is pulverized with the cutting and grinding appearance or shredded with scissors; Take by weighing the 1.0g sample in container, add the 10mL organic solvent dissolution, wherein ABS plastic is used acetone solution; The PS plastics dissolve with methylene chloride, and the PVC plastics dissolve with tetrahydrofuran; Sonic oscillation 15min; After treating dissolving fully, drip 10mL methyl alcohol, jolting to plastic matrix deposition fully; Solution is moved to centrifuge tube, use 5mL washed with methanol container again, be incorporated in the centrifuge tube then; 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 and crossed post liquid in the heart bottle; Solution is steamed to the 4mL at 10kPa, 35 ℃ of condition underspins, be transferred in the nitrogen blowpipe of band scale, with proper amount of acetone flushing heart bottle, be incorporated in the nitrogen blowpipe then, be settled to 5mL, supply Instrument measuring after again solution being crossed 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 the toy simultaneously; Than gas chromatography and single-stage mass spectrum; This method is highly sensitive, antijamming capability is strong, can be applicable to the toy sample analysis that the matrix background interference is serious better.
The method of measuring 16 kinds of aldoketones sensitization aromatic residual quantities in the toy simultaneously of the present invention; Develop gas phase chromatogram-ion trap tandem mass spectrometry first and measured 5-methyl-2 in the toy simultaneously; 3-acetyl butyryl, trans-the 2-heptenal, anti--2-hexenoic aldehyde dimethyl-acetal, citral, cinnamic acid, laurine, benzalacetone, 2; 4-dihydroxy-3-tolyl aldehyde, α-Yi Jiajiziluolantong, lilial, 6; 10-dimethyl-3; 5, the method for 9-11 triolefins-2-ketone, 4-(4-anisyl)-3-butene-2-ketone, alpha-amyl cinnamic aldehyde, lyral, 1-(4-anisyl)-1-penten-3-one, 16 kinds of sensitization aromatic of jasminolene residual quantity has been 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 qualitative and quantitative, has qualitative, quantitative ability preferably to the toy sample of matrix more complicated; 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 doing matrix than complicated sample, and the qualitative, quantitative ability limits to some extent.And GC-MS/MS can get rid of the matrix background interference preferably, thereby increases the qualitative, quantitative ability greatly.
Embodiment
For further specifying the present invention, specify in conjunction with following examples:
1, sample pre-treatments
Cloth suede and paster toy: the toy sample is shredded to 5mm * 5mm mixing with scissors.Accurately take by weighing 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, the jam-pack bottle stopper seals film and seals, ultrasonic Extraction 20min under the room temperature.Draw supernatant in the extract, air feed phase chromatogram-ion trap mass spectrometry is measured behind the 0.45 μ m micropore PTFE filter membrane excessively.
Plastic toy: the toy sample is pulverized with the cutting and grinding appearance or shredded with scissors; Take by weighing the 1.0g sample in the 50mL conical flask, (ABS plastic is used acetone solution, and the PS plastics dissolve with methylene chloride to add the 10mL agent dissolves; The PVC plastics dissolve with tetrahydrofuran), sonic oscillation 15min.After treating dissolving fully, drip 10mL methyl alcohol, jolting moves to centrifuge tube with solution until the plastic matrix deposition fully, uses 5mL washed with methanol conical flask again, be incorporated into then in the centrifuge tube, and centrifugal 8min under 13000r/min, 4 ℃ of conditions, it is for use to get settled solution.
With 5mL methyl alcohol rinse Envi-carb graphitized carbon solid phase extraction column, the settled solution after centrifugal is crossed post, the 10mL methanol-eluted fractions is collected all and is crossed post liquid in the heart bottle.Solution is steamed to the 4mL at 10kPa, 35 ℃ of condition underspins, be transferred in the nitrogen blowpipe of band scale, then with proper amount of acetone flushing heart bottle; Be incorporated in the nitrogen blowpipe; Be settled to 5mL (more than 5mL, available slow nitrogen stream blows to less than 5mL, is settled to 5mL and gets final product like solution).Supply Instrument measuring after solution crossed 0.45 μ m micropore PTFE filter membrane.
Discussion in the pre-treatment step:
A. plastic sample pre-treating method commonly used has accelerated solvent extraction, SPE, ultrasonic Extraction, microwave abstracting etc.This method is taked ultrasonic supplementary mode, utilizes suitable organic solvent that plastics are fully dissolved, and makes the plastic matrix deposition with methyl alcohol as precipitation agent then, thereby can residual organic in the plastics be extracted more fully.Method has compared the solute effect of methyl alcohol, acetone, methylene chloride, normal hexane, toluene, ethyl acetate, tetrahydrofuran, DMF, and the result finds that ABS plastic uses 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 deposition.Plastic toy matrix more complicated, the effect of SPE mainly are pigment and some other impurity of removing in the 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 impurity such as pigment on the post again fully.
B. cloth suede and paster toy samples using ultrasonic Extraction mode are extracted, and extracting back solution needs filtering membrane to remove small particle.Find in the actual detected that in most cases the solution behind acetone extraction cloth suede or the paster toy sample does not have color or very slight color, measure but go up machine behind the direct filtration film this moment; If solution colour is darker, can with methyl alcohol solution be settled to about 25mL with reference to the disposal route of plastic toy sample; SPE and to revolve the steaming condition constant; Finally be settled to 5mL, machine is measured on filtering membrane, and the result also can meet the demands.
2, gas phase chromatogram-ion trap mass spectroscopy condition
Gas chromatography is separated the actual conditions that is adopted, comprise that chromatographic column kind, temperature programme condition, sample introduction pattern etc. do not limit, 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 equivalents;
C. temperature programme: initial temperature is 50 ℃, keeps rising to 155 ℃ with 5 ℃/min speed behind the 1min, keeps 6min, rises to 280 ℃ with 3 ℃/min speed then;
D. carrier gas: high-purity helium, flow velocity are 0.7mL/min;
E. injector temperature: 280 ℃; Sample introduction pattern: split sampling not;
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. from gain control (Target TIC): 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 seen table 1.
The chromatogram of 16 kinds of materials of table 1 and mass spectrophotometry parameter
Annotate: the first-selected quota ion of the conduct of band *
3, the preparation of standard solution and standard working curve
The standard items 0.05g (being accurate to 0.1mg) that takes by weighing each material is to the brown volumetric flask of 100ml, and the acetone constant volume obtains concentration respectively and be each material list mark and the full standard inventory solution that mixes of 500mg/L, and places 4 ℃ to keep in Dark Place.During use, draw an amount of standard inventory solution as required, with the working solution of acetone diluted to respective concentration, concentration range is 0.01mg/L～50mg/L.
Under the chromatographic condition of setting, standard operation solution is measured by concentration from low to high successively, be ordinate with the peak area of the quota ion chromatographic peak that obtains, the sample introduction concentration of each corresponding material is the horizontal ordinate mapping, the drawing standard working curve.The result shows, 2, and 4-dihydroxy-3-tolyl aldehyde linearity is poor slightly, 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 is all greater than 0.9968.
Corresponding content of material is as quantitative limit during greater than 10 times of noises with response signal for this method, and when measuring cloth suede with the paster sample, the quantitative limit of confirming each material is all less than 10mg/kg, and when the mensuration plastic sample, the quantitative limit of each material is all 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 concentration repeat 6 tests.For plastic sample, modal ABS plastic toy is as blank matrix on the employing toy market.Can know that by the result between 81.2%-110.4%, relative standard deviation (RSD) is between 1.2%-9.8% for the recovery of different material for method.Concrete data are seen table 3.
The recovery of table 3 method and precision (n=6)
5, the mensuration of toy actual sample
Use this method, to from stochastic buying on the market to 5 kinds of cotton flannel toies, 5 kinds of paster toys and the 5 kinds of plastic toys mensuration of carrying out above-mentioned 16 kinds of sensitization aromatic residual quantities.Mensuration result does, detects laurine in 3 kinds of paster toys, 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 in a kind of paster toy, 10-dimethyl-3,5,9-11 triolefins-2-ketone, content are 99.8mg/kg; Detect benzalacetone in 2 kinds of plastic toys, content is respectively 1.7mg/kg and 4.6mg/kg; Detect α-Yi Jiajiziluolantong in a kind of plastic toy, content is 4.2mg/kg.All the other all do not detect.
Above-described embodiment describes preferred implementation of the present invention; Be not that 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 (4)
1. method of measuring 16 kinds of aldoketones sensitization aromatic residual quantities in the toy simultaneously is characterized in that: after the toy sample is carried out 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, or equivalents;
(2) temperature programme: initial temperature is 50 ℃, keeps rising to 155 ℃ with 5 ℃/min speed behind the 1min, keeps 6min, rises to 280 ℃ with 3 ℃/min speed then;
(3) carrier gas: high-purity helium, flow velocity are 0.7mL/min;
(4) injector temperature is 280 ℃; The sample introduction pattern is split sampling not;
(5) analysis temperature of ion trap mass spectrometry is: 220 ℃ of ion trap temperature, 50 ℃ of vacuum subassembly temperature, 280 ℃ of transmission line temperature; The ionization mode is EI; Ionizing energy is 70eV.
2. method according to claim 1; It is characterized in that: said aldoketones sensitization aromatic is 5-methyl-2; 3-acetyl butyryl, trans-the 2-heptenal, anti--2-hexenoic aldehyde dimethyl-acetal, citral, cinnamic acid, laurine, benzalacetone, 2; 4-dihydroxy-3-tolyl aldehyde, α-Yi Jiajiziluolantong, lilial, 6; 10-dimethyl-3,5,9-11 triolefins-2-ketone, 4-(4-anisyl)-3-butene-2-ketone, alpha-amyl cinnamic aldehyde, lyral, 1-(4-anisyl)-1-penten-3-one, jasminolene.
3. method according to claim 2 is characterized in that: when the toy sample was cloth suede or paster type toy sample, said pre-treatment process was: the toy sample is shredded to 5mm * 5mm mixing with scissors; Accurately take by weighing the 1.0g sample, be placed in the container, add 20mL acetone as extracting solvent, closed container, ultrasonic Extraction 20min under the room temperature; Draw supernatant in the extract, supply behind the 0.45 μ m micropore PTFE filter membrane excessively to measure.
4. method according to claim 2; It is characterized in that: when the toy sample was the plastic toy sample, said pre-treatment process was: the toy sample is pulverized with the cutting and grinding appearance or shredded with scissors, take by weighing the 1.0g sample in container; Add the 10mL organic solvent dissolution; Wherein ABS plastic is used acetone solution, and the PS plastics dissolve with methylene chloride, and the PVC plastics dissolve with tetrahydrofuran; Sonic oscillation 15min; After treating dissolving fully, drip 10mL methyl alcohol, jolting to plastic matrix deposition fully; Solution is moved to centrifuge tube, use 5mL washed with methanol container again, be incorporated in the centrifuge tube then; 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 and crossed post liquid in the heart bottle; Solution is steamed to the 4mL at 10kPa, 35 ℃ of condition underspins, be transferred in the nitrogen blowpipe of band scale, with proper amount of acetone flushing heart bottle, be incorporated in the nitrogen blowpipe then, be settled to 5mL, supply Instrument measuring after again solution being crossed 0.45 μ m micropore PTFE filter membrane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110355869.4A CN102393438B (en) | 2011-11-10 | 2011-11-10 | Method for simultaneously determining residual quantities of sixteen sensitized aldehyde and ketone perfumes in toy |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110355869.4A CN102393438B (en) | 2011-11-10 | 2011-11-10 | Method for simultaneously determining residual quantities of sixteen sensitized aldehyde and ketone perfumes in toy |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102393438A true CN102393438A (en) | 2012-03-28 |
| CN102393438B CN102393438B (en) | 2014-01-08 |
Family
ID=45860797
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110355869.4A Expired - Fee Related CN102393438B (en) | 2011-11-10 | 2011-11-10 | Method for simultaneously determining residual quantities of sixteen sensitized aldehyde and ketone perfumes in toy |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102393438B (en) |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103235054A (en) * | 2013-04-17 | 2013-08-07 | 宁波检验检疫科学技术研究院 | Method for determining banned and restricted compounds in toys with accelerated solvent extraction and gas chromatograph-mass spectrometer |
| 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 |
| CN106770800A (en) * | 2017-02-21 | 2017-05-31 | 中国检验检疫科学研究院 | 58 kinds of method for quick of sensitization aromatic in a kind of articles for children |
| 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 |
| CN106990174A (en) * | 2017-02-21 | 2017-07-28 | 中国检验检疫科学研究院 | SVOC quick determination methods in a kind of cloth velvet sample based on full volatilization head space |
| CN108828102A (en) * | 2018-08-20 | 2018-11-16 | 云南同创检测技术股份有限公司 | A kind of method of allyl cyclohexyl propionate and jasmine aldehyde in measurement flavors and fragrances |
| CN109541083A (en) * | 2019-01-30 | 2019-03-29 | 广州质量监督检测研究院 | The method for detecting volatile flavor substance in polrvinyl chloride product |
| CN110702920A (en) * | 2019-10-14 | 2020-01-17 | 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 |
| CN112034072A (en) * | 2020-09-12 | 2020-12-04 | 河南牧业经济学院 | Method for measuring content and condensation degree of citral diacetal and lauraldehyde diacetal in perfume through gas chromatography-tandem mass spectrometry |
| CN112098543A (en) * | 2020-08-31 | 2020-12-18 | 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 |
| 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 |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102175791A (en) * | 2011-01-12 | 2011-09-07 | 上海安谱科学仪器有限公司 | Method for detecting multiple allergic aroma agents in toys |
-
2011
- 2011-11-10 CN CN201110355869.4A patent/CN102393438B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102175791A (en) * | 2011-01-12 | 2011-09-07 | 上海安谱科学仪器有限公司 | Method for detecting multiple allergic aroma agents in toys |
Non-Patent Citations (2)
| Title |
|---|
| S. C. RASTOGI ETAL: "Fragrance chemicals in domestic and occupational products", 《CONTACT DERMATITIS》 * |
| 于文佳 等: "基于解卷积报告软件数据库的GC/MS方法快速确证玩具中160多种有毒有害有机物质", 《分析实验室》 * |
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103235054B (en) * | 2013-04-17 | 2014-09-10 | 宁波检验检疫科学技术研究院 | Method for determining banned and restricted compounds in toys with accelerated solvent extraction and gas chromatograph-mass spectrometer |
| CN103235054A (en) * | 2013-04-17 | 2013-08-07 | 宁波检验检疫科学技术研究院 | Method for determining banned and restricted compounds in toys with accelerated solvent extraction and gas chromatograph-mass spectrometer |
| 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 |
| 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 |
| CN106770800A (en) * | 2017-02-21 | 2017-05-31 | 中国检验检疫科学研究院 | 58 kinds of method for quick of sensitization aromatic in a kind of articles for children |
| CN106990174A (en) * | 2017-02-21 | 2017-07-28 | 中国检验检疫科学研究院 | SVOC quick determination methods in a kind of cloth velvet sample based on full volatilization head space |
| 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 |
| 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 |
| CN108828102A (en) * | 2018-08-20 | 2018-11-16 | 云南同创检测技术股份有限公司 | A kind of method of allyl cyclohexyl propionate and jasmine aldehyde in measurement flavors and fragrances |
| CN109541083A (en) * | 2019-01-30 | 2019-03-29 | 广州质量监督检测研究院 | The method for detecting volatile flavor substance in polrvinyl chloride product |
| 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 |
| CN110702920A (en) * | 2019-10-14 | 2020-01-17 | 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 |
| CN112098543A (en) * | 2020-08-31 | 2020-12-18 | 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 |
| 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 |
| CN112034072A (en) * | 2020-09-12 | 2020-12-04 | 河南牧业经济学院 | Method for measuring content and condensation degree of citral diacetal and lauraldehyde diacetal in perfume through 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102393438B (en) | 2014-01-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102393438B (en) | Method for simultaneously determining residual quantities of sixteen sensitized aldehyde and ketone perfumes in toy | |
| CN103105437B (en) | Method for simultaneous determination of residual quantity of 8 ester allergenic aromatics in toys | |
| CN103105438B (en) | Method for simultaneously detecting residual amounts of 13 phenolic alcohol sensitization aromatics in toy | |
| CN101598707B (en) | Method for detecting various pesticide residue in oil-containing food | |
| CN102507823B (en) | Method for determining content of phthalate in paper material for cigarette | |
| Wang et al. | Construction of uniformly sized pseudo template imprinted polymers coupled with HPLC–UV for the selective extraction and determination of trace estrogens in chicken tissue samples | |
| CN106324130A (en) | Chiral analysis method for nicotine in cigarette cut tobacco | |
| CN106290682B (en) | Chiral analysis method of nicotine in tea | |
| CN103076411A (en) | Analytical method for determining aromatic constituents in tea | |
| CN102608225B (en) | Determination method of harmful organic substance residue in toy sample | |
| CN102998381A (en) | Method for measuring content of phthalic acid ester in tipping paper for cigarettes | |
| CN104931605B (en) | Method for detecting quality of pepper powder based on component analysis | |
| CN108693257A (en) | The method for directly detecting tealeaves glucosides bound state aroma precursor substance | |
| KR100927463B1 (en) | Simultaneous determination of methamphetamine, amphetamine, 3,4-methylenedioxymethylamphetamine, 3,4-methylenedioxyamphetamine, and norketamine in hair | |
| CN104101662A (en) | Metabonomics method for testing terpenoids in fresh tobacco leaves | |
| CN110161165A (en) | It is a kind of while detecting the analysis method of polycyclic aromatic hydrocarbon and its Metabolism of hydroxyl content level in hair | |
| CN105158392A (en) | Method for determining special tobacco N-nitrosamine in cigarette liquid of electronic cigarette | |
| CN106645444B (en) | A kind of method of multiring aromatic hydrocarbon substance content in detection smoke-free tobacco product | |
| CN106442753B (en) | A kind of method of TSNAs content in measurement cigarette mainstream flue gas | |
| CN104535695A (en) | Method for simultaneously detecting phenol, NNK and benzo-[a]-pyrene in main stream smoke of cigar by using gas chromatography-tandem mass spectrum | |
| CN101865889A (en) | Method for determining benzo [a] pyrene in cigarette side-stream fume | |
| CN109459506A (en) | A kind of quick sample pretreatment method detected for Polychlorinated biphenyls in tealeaves | |
| CN103149311B (en) | Measuring method of sesame phenol content in tobacco essence perfume | |
| CN106841498B (en) | A kind of method for measuring tobacco and tobacco product abienol | |
| CN104849385B (en) | Gas chromatographic mass spectrometry determination method for chlorobenzene compounds |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20140108 Termination date: 20141110 |
|
| EXPY | Termination of patent right or utility model |