CN105911199A - Method for detecting karanal in washing product - Google Patents
Method for detecting karanal in washing product Download PDFInfo
- Publication number
- CN105911199A CN105911199A CN201610463589.8A CN201610463589A CN105911199A CN 105911199 A CN105911199 A CN 105911199A CN 201610463589 A CN201610463589 A CN 201610463589A CN 105911199 A CN105911199 A CN 105911199A
- Authority
- CN
- China
- Prior art keywords
- sample
- karanal
- extraction
- washing
- articles
- 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
- 0 CCC(CC1P)=CCC1C(OC1)OCC1(*)C(*)CSC Chemical compound CCC(CC1P)=CCC1C(OC1)OCC1(*)C(*)CSC 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/88—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86
Landscapes
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
Abstract
The invention relates to a method for detecting karanal in a washing product, and belongs to the technical field of chemical and commodity inspection .The method comprises the steps of sample preparation, sample pretreatment, sample detecting confirmation and detecting result calculating and presenting. Solid, semisolid and powdery samples are subjected to supersonic extraction with methyl alcohol or acetonitrile, lead acetate is used for precipitating and purifying a matrix, and normal hexane liquid is concentrated, sized and analyzed after extraction. Liquid samples are mixed to be uniform through volution for extraction, lead acetate is used for precipitating and purifying a matrix, volution is carried out, and normal hexane liquid is concentrated, sized and analyzed after extraction. The method has the advantages of being short in pretreatment time, high in efficiency, good in method stability and the like, and the fast detection requirements of karanal in the washing product can be met. Meanwhile, the set standard requirement put forward by Certification and Accreditation Administration is met and exceeded on the aspect of limit of detection, reproducibility and other indexes inspected by the technology, and the method can become an alternative of the industrial standard method.
Description
Technical field
The invention belongs to chemicals and commodity inspection technical field, be more particularly to the detection method of karanal in a kind of articles for washing.
Background technology
Karanal, has another name called 2-(2,4-dimethyl-3-cyclohexyl)-5-methyl-5-(1-methyl-propyl)-1, and 3-dioxy oxane, molecular formula is: C17H30O2, CAS registration number: 117933-89-8, for colourless transparent liquid, its density is 0.928g/cm3, and under 101kpa, boiling point is 329.9 DEG C, and flash-point is 165.8 DEG C, and at 25 DEG C, vapour pressure is 0.000044023kpa, it is difficult to volatilization.Karanal is the fragrance raw material with the dry imperial saliva Radix Aucklandiae, has outstanding fabric lasting ability, is widely used in the daily products such as toy, textile, soap, detergent, fabric softening agent.Owing to this material has high persistency and high bioaccumulation, human body and environment being likely to result in harm, EU REACH Legislation has been listed in the 13rd batch of high concern list of substances, and the typical isomers structure of its molecule is shown in following (I) formula.
Currently, this kind of material examination criteria during China lacks more comprehensive articles for washing.The document report detection method referred to lacks.Current related art is: number of patent application is " detection method of karanal in a kind of personal-care supplies " of 201510397187.8, the method discloses personal-care supplies sample and uses distilled water extraction, normal hexane liquid-liquid extraction, will use gas chromatography/mass spectrometry after the normal hexane leafing heart.
Although above-mentioned prior art can solve the test problems of part karanal, but all there is certain defect.(1) Extraction solvent used is incorrect.The methyl of low pole and hexatomic ring skeleton in karanal molecular structure, do not contain the hydroxyl of polarity, amino isopolarity group, polarity is more weak, principle according to material " similar mix ", karanal is easier to be dissolved in the personal-care supplies substrate containing lipid component, rather than it is dissolved in as in the water of extractant, especially for the solid such as fancy soap, cold cream and semi-solid sample, the penetration power of water is poor, its disclosed method can not preferably be extracted, and the water therefore using non-organic solvent is not ideal chose as extractant；(2) necessary purification means are lacked.Personal-care supplies main component has hydro carbons and Ester that part can be dissolved in the water, when using normal hexane that aqueous extract is carried out liquid-liquid extraction, this partial impurities will be dissolved in normal hexane layer, thus will pollute chromatographic mass spectrometry system after sample introduction, shorten chromatographic column service life.
The present situation of karanal examination criteria method in articles for washing is lacked for current, and above-mentioned prior art Extraction solvent is incorrect, lack necessary purification means and may bring the problem of infringement to instrument and chromatographic column, the present invention proposes a kind of gas chromatography-mass spectrography detection method that can quickly detect karanal in articles for washing.The substrate range of method defined meets requirement both domestic and external, and detection limit reaches the limitation requirement arranged both at home and abroad, meets methodological study key element, has the good suitability, stability and reliability.
Summary of the invention
Lacking the problem such as karanal detection method and the deficiencies in the prior art in articles for washing for current, the present invention proposes the detection method of karanal in a kind of articles for washing.
The present invention is to solve above-mentioned technical problem by the following technical programs.
The detection method of karanal in a kind of articles for washing, including preparation, the pre-treatment of sample, sample detection confirmation and the calculating of testing result and the statement of sample, wherein:
(1) for the extraction of solid-state, semisolid and pulverized specimen: add extracting solution, vortex, supersound extraction in the centrifuge tube claiming sample, add lead acetate solid, vortex, adds normal hexane, vibration, is centrifuged, collect whole supernatant, rotary evaporated to dryness, constant volume, to be analyzed after filtration；
(2) for the extraction of liquid sample: add extracting solution in the centrifuge tube claiming sample, vortex mixing is extracted, and adds lead acetate solid, vortex, adds normal hexane, and vibration is centrifugal, collects whole supernatant, rotary evaporated to dryness, and constant volume is to be analyzed after filtration.
Described sample weighting amount is 1.00～2.00g, is accurate to 0.001g.
Described extraction solution is methanol or acetonitrile, it is therefore preferable to acetonitrile, and extracting solution consumption is 20～30mL.
The consumption of described lead acetate is 1.0～2.0g, and normal hexane consumption is 10～15mL.
Described constant volume liquid be consumption be 2.00mL, constant volume liquid kind is acetone, toluene or dimethylbenzene, preferably dimethylbenzene.
The described supersound extraction time 20～30min, centrifugal rotational speed is 2500～4500r/min, centrifugation time 3～5min, and vortex time is 1～3min, and duration of oscillation is 15～30min, and rotating evaporation temperature is 40～50 DEG C, and filter membrane aperture is 0.22～0.45 μm.
It is an advantage of the current invention that:
(1) present invention is with articles for washing for detection substrate, provide the gas chromatography-mass spectrography detection method of karanal in a kind of articles for washing, method has the plurality of advantages such as the pre-treatment time is short, efficiency is high, method good stability, can meet the quick testing requirement of karanal in articles for washing；Meanwhile, all reach and strictly in recognizing the formulation standard-required that prison committee proposes in terms of the indexs such as detection limit, repeatability, fully meet methodological study requirement, the alternative of industry standard methods can be become.
(2) present invention is according to the molecular structure feature of karanal, uses organic solvent that solid, semisolid and pulverized specimen carry out supersound extraction and can improve extraction efficiency, and can increase sample weighting amount, makes detection obtain relatively reliable result.
(3) present invention uses lead acetate as precipitant, the most impurity in extraction solution can be made to produce precipitation, reach the effect effectively purified sample extracting solution, thus reduce the impurity infringement to chromatograph mass spectrometer system.
Accompanying drawing explanation
Fig. 1 is the total ion current figure of karanal standard solution, and wherein chromatographic peak 1-6 is the isomer that karanal is different；
Fig. 2 is the mass spectrum of karanal standard solution；
Fig. 3 is the clean-up effect figure of different sample substrate, and wherein A is standard solution, and B is blank experiment, and C is for adding target detergent sample, and D is for adding target cleaning mixture sample, and E is positive cleaning mixture sample, and wherein sample adds concentration is 15.0mg/kg.
Detailed description of the invention
For the openest rather than restriction present invention, below in conjunction with example, the present invention is described in further detail.
Reagent chemicals involved in the embodiment of the present invention is as follows:
Outside unless otherwise prescribed, reagent is the above reagent of analytical pure.
Karanal standard substance: purity is more than or equal to 98.0%.
Embodiment 1
Matrix sample is detergent
The preparation of 1 sample and title sample:
Prepared by 1.1 samples
Detergent sample blending.Load in clean container, airtight, indicate labelling, cryopreservation.
1.2 claim sample
Sample 1.00g (being accurate to 0.001g), pending pre-treatment is accurately weighed in the tool plug centrifuge tube of 50mL.
The pre-treatment of 2 samples:
20mL methanol is added in the above-mentioned centrifuge tube having claimed sample, vortex 1mim, supersound extraction 30min, add lead acetate solid 1.00g, vortex 1min, adding normal hexane 15mL, vibration 15min, rotating speed 4500r/min are centrifuged 3min, collect whole supernatant, rotary evaporated to dryness at 40 DEG C, adds 2.00mL acetone constant volume, to be analyzed after crossing 0.22 μm filter membrane.3 chromatography-mass spectroscopy testing conditions:
3.1 chromatographic columns: DB-5MS capillary column, 30m × 0.25mm (internal diameter), 0.25 μm.
3.2 heating schedules: 60 DEG C keep 1min, with 12 DEG C/min ramp to 200 DEG C, keep 7min.
3.3 injector temperatures: 280 DEG C.
3.4 chromatographic mass spectrometry interface temperature: 280 DEG C.
3.5 ionization mode: EI (70ev).
3.6 ion source temperatures: 230 DEG C.
3.7 carrier gas: helium, purity is more than 99.999%, flow velocity 1.0mL/min.
3.8 input modes: do not shunt；
3.9 sample sizes: 1 μ L.
3.10 mensuration modes: Salbutamol Selected Ion Monitoring (SIM).
3.11 select monitoring ion (m/z): 120.1,107.1,157.1,251.2 (abundance ratio is: 100-74-54-20)；
3.12 solvent delay: 10min.
4 sample detection and confirmation
The preparation of 4.1 standard working curves:
Take appropriate OK a karaoke club aldehyde standard substance, be settled to 50.0mL with acetone and be configured to 1000mg/L standard reserving solution, save backup in-4 DEG C of refrigerators.
Pipette respectively the standard reserving solution of 1000mg/L with acetone soln be diluted to concentration as 1mg/L, the karanal standard working solution of 2mg/L, 10mg/L, 20mg/L, 100mg/L.The most accurately draw 1 μ L injection gas chromatography-mass spectrograph to be analyzed, test according to above-mentioned chromatography-mass spectroscopy testing conditions.With the concentration of standard substance as abscissa, peak area is that vertical coordinate draws standard working curve.
4.2 qualitatively and quantitatively analyze
According to measured object content situation in final analysis liquid to be measured, the standard working solution of selected concentration comparable, standard working solution and sample liquid equal-volume ginseng is injected sample measure, standard specimen working solution and treat that in sample measuring liquid, the response value of the mensuration of karanal content all should be in the range of linearity of instrument detection.
If in the selection chromatography of ions figure of sample liquid and standard working solution, chromatographic peak is had to occur in identical retention time (± 0.05min), and in the sample mass spectrum after background correction, selected ion all occurs, the abundance ratio of the abundance ratio ion corresponding with standard substance of selected ion, its value is in allowed band.According to quota ion, object is carried out quantified by external standard method.Under the testing conditions optimized, the standard solution total ions chromatogram of object is shown in that Fig. 2 and full scan mass spectrum see Fig. 3.
Relative to the abundance of ions margin of error when table 1 uses qualitative gas chromatography-mass spectrum
4.3 blank experiment
In addition to not weighing sample, remaining is all carried out by pre-treatment step.
The calculating of 5 testing results and statement:
With chromatographic data processor or by object residual quantity in formula (1) calculating sample:
In formula:
The residual quantity of object in X sample, unit is milligrams per kilogram (mg/kg)；
The chromatographic peak area of object in S sample liquid；
SsThe chromatographic peak area of object in standard working solution；
The concentration of object in c standard working solution, unit is micrograms per millilitre (μ g/mL)；
The final constant volume of V sample liquid, unit is milliliter (mL)；
Sample mass representated by m final samples liquid, unit is gram (g)；
6 measure the range of linearity of detergent sample, linear equation, correlation coefficient, detection limit and quantitative limit is shown in Table 2；
The linear equation of karanal in table 2 detergent, correlation coefficient, the range of linearity, detection limit and quantitative limit
7 under 1,2 and 10mg/kg tri-spiked levels levels, and the response rate and precision that each horizontal checkout is six times are as shown in table 3:
The recovery of standard addition of karanal and precision (n=6) in table 3 detergent
8 Fig. 3 show the clean-up effect comparison diagram of mark-on detergent.
Embodiment 2
Sample substrate is cleaning mixture
The preparation of 1 sample and title sample:
Prepared by 1.1 samples
Cleaning mixture sample blending.Load in clean container, airtight, indicate labelling, cryopreservation.
1.2 claim sample
Sample 2.00g (being accurate to 0.001g), pending pre-treatment is accurately weighed in the tool plug centrifuge tube of 50mL.
The pre-treatment of 2 samples:
30mL methanol is added in the above-mentioned centrifuge tube having claimed sample, 3mim is extracted in vortex mixing, add lead acetate solid 2.00g, vortex 1min, add normal hexane 20mL, vibration 15min, rotating speed 2500r/min is centrifuged 3min, collects whole supernatant, rotary evaporated to dryness at 50 DEG C, add 2.00mL dimethylbenzene constant volume, to be analyzed after crossing 0.45 μm filter membrane.
3 chromatography-mass spectroscopy testing conditions:
3.1 chromatographic columns: DB-5MS capillary column, 30m × 0.25mm (internal diameter), 0.25 μm.
3.2 heating schedules: 60 DEG C keep 1min, with 12 DEG C/min ramp to 200 DEG C, keep 7min.
3.3 injector temperature: 280 DEG C.
3.4 chromatographic mass spectrometry interface temperature: 280 DEG C.
3.5 ionization mode: EI (70ev).
3.6 ion source temperatures: 230 DEG C.
3.7 carrier gas: helium, purity is more than 99.999%, flow velocity 1.0mL/min.
3.8 input modes: do not shunt；
3.9 sample sizes: 1 μ L.
3.10 mensuration modes: Salbutamol Selected Ion Monitoring (SIM).
3.11 select monitoring ion (m/z): 120.1,107.1,157.1,251.2 (abundance ratio is: 100-74-54-20)；
3.12 solvent delay: 10min.
4 sample detection and confirmation
The preparation of 4.1 standard working curves:
Take appropriate OK a karaoke club aldehyde standard substance, be settled to 50.0mL with acetone and be configured to 1000mg/L standard reserving solution, save backup in-4 DEG C of refrigerators.
Pipette respectively the standard reserving solution of 1000mg/L with acetone soln be diluted to concentration as 1mg/L, the karanal standard working solution of 2mg/L, 10mg/L, 20mg/L, 100mg/L.The most accurately draw 1 μ L injection gas chromatography-mass spectrograph to be analyzed, test according to above-mentioned chromatography-mass spectroscopy testing conditions (step 3).With the concentration of standard substance as abscissa, peak area is that vertical coordinate draws standard working curve.
4.2 qualitatively and quantitatively analyze
According to measured object content situation in final analysis liquid to be measured, the standard working solution of selected concentration comparable, standard working solution and sample liquid equal-volume ginseng is injected sample measure, standard specimen working solution and treat that in sample measuring liquid, the response value of the mensuration of karanal content all should be in the range of linearity of instrument detection.
If in the selection chromatography of ions figure of sample liquid and standard working solution, chromatographic peak is had to occur in identical retention time (± 0.05min), and in the sample mass spectrum after background correction, selected ion all occurs, the abundance ratio of the abundance ratio ion corresponding with standard substance of selected ion, its value, in allowed band, is shown in Table 1.According to quota ion, object is carried out quantified by external standard method.4.3 blank experiment
In addition to not weighing sample, remaining is all carried out by pre-treatment step.
The calculating of 5 testing results and statement:
With chromatographic data processor or by object residual quantity in formula (1) calculating sample:
In formula:
The residual quantity of object in X sample, unit is milligrams per kilogram (mg/kg)；
The chromatographic peak area of object in S sample liquid；
SsThe chromatographic peak area of object in standard working solution；
The concentration of object in c standard working solution, unit is micrograms per millilitre (μ g/mL)；
The final constant volume of V sample liquid, unit is milliliter (mL)；
Sample mass representated by m final samples liquid, unit is gram (g)；
6 measure the range of linearity of cleaning mixture sample, linear equation, correlation coefficient, detection limit and quantitative limit is shown in Table 4；
The linear equation of karanal in table 4 cleaning mixture, correlation coefficient, the range of linearity, detection limit and quantitative limit
7 under 1,2 and 10mg/kg tri-spiked levels levels, and the response rate and precision that each horizontal checkout is six times are as shown in table 5:
The recovery of standard addition of karanal and precision (n=6) in table 5 cleaning mixture
8 Fig. 3 show mark-on cleaning mixture and the clean-up effect comparison diagram of positive cleaning mixture.
Embodiment described above only have expressed embodiments of the present invention, and it describes more concrete and detailed, but therefore can not be interpreted as the restriction to the scope of the claims of the present invention.It should be noted that; for the ordinary skill in the art, without departing from the inventive concept of the premise, it is also possible to make some deformation and improvement; these belong to protection scope of the present invention, and the protection domain of patent the most of the present invention should be as the criterion with claims.
Claims (6)
1. a detection method for karanal in articles for washing, including preparation, the pre-treatment of sample, sample detection confirmation and the calculating of testing result and the statement of sample, it is characterised in that:
(1) for the extraction of solid-state, semisolid and pulverized specimen: add extracting solution, vortex, supersound extraction in the centrifuge tube claiming sample, add lead acetate solid, vortex, adds normal hexane, vibration, is centrifuged, collect whole supernatant, rotary evaporated to dryness, constant volume, to be analyzed after filtration；
(2) for the extraction of liquid sample: add extracting solution in the centrifuge tube claiming sample, vortex mixing is extracted, and adds lead acetate solid, vortex, adds normal hexane, and vibration is centrifugal, collects whole supernatant, rotary evaporated to dryness, and constant volume is to be analyzed after filtration.
The detection method of karanal in articles for washing the most according to claim 1, it is characterised in that described sample weighting amount is 1.00～2.00g, is accurate to 0.001g.
The detection method of karanal in articles for washing the most according to claim 1, it is characterised in that described extraction solution is methanol or acetonitrile, it is therefore preferable to acetonitrile, extracting solution consumption is 20～30mL.
The detection method of karanal in articles for washing the most according to claim 1, it is characterised in that the consumption of described lead acetate is 1.0～2.0g, normal hexane consumption is 10～15mL.
The detection method of karanal in articles for washing the most according to claim 1, it is characterised in that described constant volume liquid be consumption be 2.00mL, constant volume liquid kind is acetone, toluene or dimethylbenzene, preferably dimethylbenzene.
The detection method of karanal in articles for washing the most according to claim 1, it is characterized in that, the described supersound extraction time 20～30min, centrifugal rotational speed is 2500～4500r/min, centrifugation time 3～5min, vortex time is 1～3min, and duration of oscillation is 15～30min, rotating evaporation temperature is 40～50 DEG C, and filter membrane aperture is 0.22～0.45 μm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610463589.8A CN105911199B (en) | 2016-06-23 | 2016-06-23 | The detection method of karanal in a kind of articles for washing |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610463589.8A CN105911199B (en) | 2016-06-23 | 2016-06-23 | The detection method of karanal in a kind of articles for washing |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105911199A true CN105911199A (en) | 2016-08-31 |
| CN105911199B CN105911199B (en) | 2019-10-15 |
Family
ID=56758412
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610463589.8A Expired - Fee Related CN105911199B (en) | 2016-06-23 | 2016-06-23 | The detection method of karanal in a kind of articles for washing |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105911199B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110095548A (en) * | 2019-06-05 | 2019-08-06 | 广东产品质量监督检验研究院（国家质量技术监督局广州电气安全检验所、广东省试验认证研究院、华安实验室） | The measuring method of karanal isomer total content in a kind of coating |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102432588A (en) * | 2011-11-25 | 2012-05-02 | 河南科技大学 | Method for synthesizing karanal |
| CN105044261A (en) * | 2015-07-02 | 2015-11-11 | 深圳市谱尼测试科技有限公司 | Method for detecting karanal in personal care product |
| CN105259281A (en) * | 2015-07-22 | 2016-01-20 | 谱尼测试科技(天津)有限公司 | Method for determination of karanal content of plastic toy material |
-
2016
- 2016-06-23 CN CN201610463589.8A patent/CN105911199B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102432588A (en) * | 2011-11-25 | 2012-05-02 | 河南科技大学 | Method for synthesizing karanal |
| CN105044261A (en) * | 2015-07-02 | 2015-11-11 | 深圳市谱尼测试科技有限公司 | Method for detecting karanal in personal care product |
| CN105259281A (en) * | 2015-07-22 | 2016-01-20 | 谱尼测试科技(天津)有限公司 | Method for determination of karanal content of plastic toy material |
Non-Patent Citations (2)
| Title |
|---|
| 王亚吨 等: "反相高效液相色谱法测定饲料中三聚氰胺的含量", 《广东饲料》 * |
| 王璐 等: "烟草中主要糖的高效液相色谱测定研究", 《云南大学学报（自然科学版）》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110095548A (en) * | 2019-06-05 | 2019-08-06 | 广东产品质量监督检验研究院（国家质量技术监督局广州电气安全检验所、广东省试验认证研究院、华安实验室） | The measuring method of karanal isomer total content in a kind of coating |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105911199B (en) | 2019-10-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Vallecillos et al. | Fully automated ionic liquid-based headspace single drop microextraction coupled to GC–MS/MS to determine musk fragrances in environmental water samples | |
| CN102175785B (en) | Method for detecting VOC (Volatile Organic Compound) matters in toy paint | |
| CN105784894B (en) | Pesticide residue detection method for traditional Chinese medicine | |
| KR100927463B1 (en) | Simultaneous determination of methamphetamine, amphetamine, 3,4-methylenedioxymethylamphetamine, 3,4-methylenedioxyamphetamine, and norketamine in hair | |
| CN110596256A (en) | Method for simultaneously detecting glycidyl ester and chloropropanol ester in food | |
| CN102520079A (en) | Method for rapidly measuring content of solanesol in tobaccos by using UPLC (Ultra Performance Liquid Chromatography) | |
| CN111595956B (en) | Method for detecting hormone and neurotransmitter in serum | |
| Monperrus et al. | Rapid, accurate and precise determination of tributyltin in sediments and biological samples by species specific isotope dilution-microwave extraction-gas chromatography-ICP mass spectrometry | |
| CN111122760A (en) | Method for extracting volatile components from plants based on natural eutectic solvent pretreatment-headspace solid phase microextraction | |
| Polettini et al. | Rapid and highly selective GC/MS/MS detection of heroin and its metabolites in hair | |
| CN105911199A (en) | Method for detecting karanal in washing product | |
| CN109975451B (en) | Method for extracting and analyzing plant volatile components | |
| CN113866336B (en) | Integrated detection method for safrole and dihydrosafrole in ginger and ginger powder | |
| CN113671093A (en) | Method for rapidly detecting p-hydroxybenzoic acid substances in human urine | |
| Wei et al. | Dispersive liquid-liquid microextraction for simultaneous determination of six parabens in aqueous cosmetics | |
| CN104502486B (en) | A kind of apply the method for methyl vanillin and ethyl vanillin in Headspace-solid phase microextraction technical measurement milk powder | |
| CN103217498A (en) | Method for detecting dicyandiamide in milk powder with LC-MS (liquid chromatography/mass spectrometry) and sample preparation method | |
| Ottoila et al. | Quantitative determination of nitroglycerin in human plasma by capillary gas chromatography negative ion chemical ionization mass spectrometry | |
| CN101825617A (en) | Method for measuring stable components in medicine by adopting gas chromatography/ mass spectrometry and efficient liquid chromatography | |
| CN106053694A (en) | Method for detecting residual amount of 2,6-diisopropylnaphthalene in food | |
| CN103558300B (en) | Soporific and sedative drug inspection method for treating biological detection material by using gel permeation chromatography | |
| CN107632082B (en) | Method for measuring alkaloid components in zanthoxylum armatum medicinal material | |
| Lee et al. | Rapid HPLC method for the simultaneous determination of eight urinary metabolites of toluene, xylene and styrene | |
| CN103344715A (en) | Method for separation and enrichment of penicillin antibiotics in water | |
| CN113640401B (en) | Method for detecting aristolochic acid in soil |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20190917 Address after: 350300 China Customs Building, 299 Qingrong Avenue, Fuzhou City, Fujian Province Applicant after: Ding Liping Applicant after: INTEGRATED TECHNICAL SERVICE CENTER, FUQING ENTY-EXIT INSPECTION & QUARANTINE BUREAU Address before: Fuqing City, Fuzhou city in Fujian province 350300 Yin Xi Zhen Qing Rong port Park Avenue Applicant before: INTEGRATED TECHNICAL SERVICE CENTER, FUQING ENTY-EXIT INSPECTION & QUARANTINE BUREAU |
|
| TA01 | Transfer of patent application right | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20191015 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |