CN105911199B - The detection method of karanal in a kind of articles for washing - Google Patents
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- CN105911199B CN105911199B CN201610463589.8A CN201610463589A CN105911199B CN 105911199 B CN105911199 B CN 105911199B CN 201610463589 A CN201610463589 A CN 201610463589A CN 105911199 B CN105911199 B CN 105911199B
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- 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
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- 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
Abstract
The present invention relates to a kind of detection methods of karanal in articles for washing, belong to chemicals and commodity inspection technical field.Method includes the preparation of sample, the pre-treatment of sample, the calculating and statement of sample detection confirmation and testing result, methanol or acetonitrile ultrasonic extraction wherein are used for solid-state, semisolid and pulverized specimen, acetate lead precipitation decontamination substrate, concentration, constant volume, analysis after n-hexane liquid-liquid extraction；Liquid sample is extracted using being vortexed to mix, acetate lead precipitation decontamination substrate is vortexed, concentration, constant volume, analysis after n-hexane liquid-liquid extraction.Method of the invention have the pre-treatment time it is short, high-efficient, method stability is good many advantages, such as, be able to satisfy the quick testing requirements of karanal in articles for washing；Meanwhile reaching in terms of the methods of detection limit, reproducibility learn the index investigated and strictly in recognizing the formulation standard requirements supervising committee and proposing, the alternative of industry standard methods can be become.
Description
Technical field
The invention belongs to chemicals and commodity inspection technical field, it is more particularly to karanal in a kind of articles for washing
Detection method.
Background technique
Karanal also known as 2- (2,4- dimethyl -3- cyclohexyl) -5- methyl -5- (1- methyl-propyl) -1,3- dioxy are disliked
Alkane, molecular formula are as follows: C17H30O2, CAS registration number: 117933-89-8, be colourless transparent liquid, density 0.928g/cm3,
Boiling point is 329.9 DEG C under 101kpa, and flash-point is that vapour pressure is 0.000044023kpa at 165.8 DEG C, 25 DEG C, it is difficult to be volatilized.Card
Garland aldehyde is the fragrance raw material with dry imperial saliva radix aucklandiae, has outstanding fabric lasting ability, is widely used in toy, spins
In the daily products such as fabric, soap, washing powder, fabric softening agent.Since the substance has high persistence and high bioaccumulation,
Harm may cause to human body and environment, EU REACH Legislation has been included in the 13rd batch high concern list of substances, point
The typical isomer structure of son is shown in following (I) formula.
Currently, China lacks this substance examination criteria in more comprehensive articles for washing.The document report inspection that can refer to
Survey method lacks.A kind of current related art are as follows: " personal-care supplies that number of patent application is 201510397187.8
The detection method of middle karanal ", personal-care supplies sample is disclosed in this method to be extracted using distilled water, n-hexane liquid liquid
Extraction will use gas chromatography/mass spectrometry after the n-hexane leafing heart.
Although the above-mentioned prior art can solve the test problems of part karanal, but have the defects that certain.
(1) Extraction solvent used is inappropriate.The methyl of low pole and hexa-atomic ring skeleton in karanal molecular structure are free of polarized
Hydroxyl, amino isopolarity group, polarity is weaker, and according to the principle of substance " similar to mix ", karanal is easier to be dissolved in
It in personal-care supplies matrix containing lipid component, rather than is dissolved in the water as extractant, especially for perfumed soap, shield
The penetration power of the solids such as skin cream and semi-solid sample, water is poor, disclosed by method cannot preferably extract, therefore had using non-
The water of solvent is not ideal chose as extractant；(2) lack necessary purification means.In personal-care supplies main component
The hydro carbons and Ester for having part that can be dissolved in the water, when carrying out liquid-liquid extraction to aqueous extract using n-hexane, this portion
Divide impurity that will be dissolved in n-hexane layer, so that chromatographic mass spectrometry system will be polluted after sample introduction, shortens using life of chromatographic column.
Lack the status of karanal examination criteria method and the extraction of the above-mentioned prior art in articles for washing for current
Solvent is inappropriate, the problem of lacking necessary purification means and may bringing damage to instrument and chromatographic column, and the present invention proposes one kind
The gas chromatography-mass spectrography detection method of karanal in articles for washing can quickly be detected.The substrate range of method defined
Meet requirement both domestic and external, detection limit reaches the limitation requirement being arranged both at home and abroad, meets methodological study element, has good
Applicability, stability and reliability.
Summary of the invention
The problems such as karanal detection method in current shortage articles for washing and the deficiencies in the prior art, the present invention
Propose a kind of detection method of karanal in articles for washing.
The present invention is to solve above-mentioned technical problem by the following technical programs.
The detection method of karanal, the pre-treatment of preparation, sample including sample, sample detection in a kind of articles for washing
The calculating and statement of confirmation and testing result, in which:
(1) extraction for solid-state, semisolid and pulverized specimen: adding extracting solution into the centrifuge tube for claimed sample, is vortexed,
Lead acetate solid is added in ultrasonic extraction, is vortexed, and n-hexane is added, and vibrates, centrifugation, collects whole supernatants, rotary evaporation is extremely
Dry, constant volume is to be analyzed after filtering；
(2) for the extraction of liquid sample: adding extracting solution into the centrifuge tube for claimed sample, be vortexed to mix and extract, be added
Lead acetate solid is vortexed, and n-hexane is added, and vibrates, centrifugation, collects whole supernatants, rotary evaporated to dryness, constant volume, after filtering
It is to be analyzed.
The sample weighting amount is 1.00~2.00g, is accurate to 0.001g.
The extraction solution is methanol or acetonitrile, it is therefore preferable to which acetonitrile, extracting solution dosage are 20~30mL.
The dosage of the lead acetate is 1.0~2.0g, and n-hexane dosage is 10~15mL.
The constant volume liquid is that dosage is 2.00mL, and constant volume liquid type is acetone, toluene or dimethylbenzene, preferably dimethylbenzene.
20~the 30min of ultrasonic extraction time, centrifugal rotational speed be 2500~4500r/min, centrifugation time 3~
5min, vortex time are 1~3min, and duration of oscillation is 15~30min, and rotating evaporation temperature is 40~50 DEG C, filter membrane aperture
It is 0.22~0.45 μm.
The present invention has the advantages that
(1) present invention is detection matrix with articles for washing, provides a kind of gas-chromatography-of karanal in articles for washing
Mass spectrometry detection method, method have the pre-treatment time it is short, high-efficient, method stability is good many advantages, such as, be able to satisfy and wash
Wash the quick testing requirements of karanal in articles；Meanwhile reaching in terms of detection limit, the indexs such as reproducibility and strictly in recognizing
The formulation standard requirements that prison committee proposes, fully meet methodological study requirement, can become the alternative of industry standard methods.
(2) the molecular structure feature of the invention according to karanal, using organic solvent to solid, semisolid and powdery sample
Product, which carry out ultrasonic extraction, can be improved extraction efficiency, and can increase sample weighting amount, and detection is made to obtain relatively reliable result.
(3) present invention can make to extract most impurity in solution and generate precipitating, reach using lead acetate as precipitating reagent
To the effect effectively purified to sample extracting solution, to reduce damage of the impurity to chromatographic mass spectrometry system.
Detailed description of the invention
Fig. 1 is the total ion current figure of karanal standard solution, and wherein chromatographic peak 1-6 is the different isomery of karanal
Body；
Fig. 2 is the mass spectrogram of karanal standard solution；
Fig. 3 is the clean-up effect figure of different sample substrates, and wherein A is standard solution, and B is blank assay, and C is washing for mark-on
Clothing powder sample, D are the cleaning solution sample of mark-on, and E is positive cleaning solution sample, and wherein sample addition concentration is 15.0mg/kg.
Specific embodiment
Further to disclose rather than the present invention is limited, the present invention is described in further detail below in conjunction with example.
Involved reagent chemicals are as follows in the embodiment of the present invention:
Outer unless otherwise prescribed, reagent is the pure above reagent of analysis.
Karanal standard items: purity is more than or equal to 98.0%.
Embodiment 1
Matrix sample is washing powder
The preparation of 1 sample and title sample:
The preparation of 1.1 samples
Washing powder sample blending.It is packed into clean container, it is closed, indicate label, cryo-conservation.
1.2 claim sample
Sample 1.00g (being accurate to 0.001g), pending pre-treatment are accurately weighed in the tool plug centrifuge tube of 50mL.
The pre-treatment of 2 samples:
20mL methanol is added into the above-mentioned centrifuge tube for having claimed sample, lead acetate is added in vortex 1mim, ultrasonic extraction 30min
N-hexane 15mL is added in solid 1.00g, vortex 1min, vibrates 15min, and revolving speed 4500r/min is centrifuged 3min, collects in whole
Clear liquid, the rotary evaporated to dryness at 40 DEG C, be added 2.00mL acetone constant volume, cross 0.22 μm of filter membrane after it is to be analyzed.3 chromatography-mass spectroscopies
Testing conditions:
3.1 chromatographic columns: DB-5MS capillary column, 30m × 0.25mm (internal diameter), 0.25 μm.
3.2 temperature programs: 60 DEG C of holding 1min are warming up to 200 DEG C with 12 DEG C/min rate, keep 7min.
3.3 injector temperatures: 280 DEG C.
3.4 chromatographic mass spectrometry interface temperatures: 280 DEG C.
3.5 ionization modes: EI (70ev).
3.6 ion source temperatures: 230 DEG C.
3.7 carrier gas: helium, purity are greater than 99.999%, flow velocity 1.0mL/min.
3.8 input modes: it does not shunt；
3.9 sample volumes: 1 μ L.
3.10 mensuration modes: Salbutamol Selected Ion Monitoring (SIM).
3.11 selection monitorings ion (m/z): 120.1,107.1,157.1,251.2 (abundance ratio are as follows: 100-74-54-20)；
3.12 solvent delays: 10min.
4 sample detections and confirmation
The preparation of 4.1 standard working curves:
Suitable OK a karaoke club aldehyde standard substance is taken, 50.0mL is settled to acetone and is configured to 1000mg/L standard reserving solution,
It is saved backup in -4 DEG C of refrigerators.
Pipette respectively the standard reserving solution of 1000mg/L with acetone soln be diluted to concentration for 1mg/L, 2mg/L, 10mg/L,
The karanal standard working solution of 20mg/L, 100mg/L.1 μ L injection gas chromatograph-mass spectrometer is accurately drawn respectively to be divided
Analysis, is tested according to above-mentioned chromatography-mass spectroscopy testing conditions.Using the concentration of standard substance as abscissa, peak area is vertical sits
Plotting standard working curve.
4.2 qualitatively and quantitatively analyze
According to measured object content situation in final analysis prepare liquid, the standard working solution of concentration comparable is selected, to standard
Working solution and sample liquid are joined in equal volume injects sample measurement, the measurement of karanal content in standard specimen working solution and the sample solution to be tested
Response should all be in the range of linearity that instrument detects.
If in sample liquid and the selection chromatography of ions figure of standard working solution, had in identical retention time (± 0.05min)
Chromatographic peak occurs, and in the sample mass spectrum after background correction, selected ion occurs, the abundance ratio of selected ion with
Standard items correspond to the abundance ratio of ion, and value is within the allowable range.Quantified by external standard method is carried out according to quota ion pair object.?
Under the testing conditions of optimization, the standard solution total ion chromatogram of object is shown in Fig. 2 and full scan mass spectrogram referring to Fig. 3.
With respect to the abundance of ions margin of error when table 1 uses qualitative gas chromatography-mass spectrum
4.3 blank assay
In addition to not weighing sample, remaining presses pre-treatment step progress.
The calculating and statement of 5 testing results:
Object residual quantity in sample is calculated with chromatographic data processor or by formula (1):
In formula:
X --- the residual quantity of object in sample, unit are milligrams per kilogram (mg/kg)；
S --- the chromatographic peak area of object in sample liquid；
Ss--- the chromatographic peak area of object in standard working solution；
C --- the concentration of object in standard working solution, unit are micrograms per millilitre (μ g/mL)；
V --- the final constant volume of sample liquid, unit are milliliter (mL)；
M --- sample mass representated by final sample liquid, unit are gram (g)；
The range of linearity, linear equation, related coefficient, detection limit and the quantitative limit of 6 measurement washing powder samples are shown in Table 2；
Linear equation, related coefficient, the range of linearity, detection limit and the quantitative limit of karanal in 2 washing powder of table
7 in the case where 1,2 and 10mg/kg, tri- spiked levels are horizontal, and the rate of recovery and precision that each horizontal checkout is six times are such as
Shown in table 3:
The recovery of standard addition of karanal and precision (n=6) in 3 washing powder of table
The clean-up effect comparison diagram of mark-on washing powder is shown in 8 Fig. 3.
Sample substrate is cleaning solution
The preparation of 1 sample and title sample:
The preparation of 1.1 samples
Cleaning solution sample blending.It is packed into clean container, it is closed, indicate label, cryo-conservation.
1.2 claim sample
Sample 2.00g (being accurate to 0.001g), pending pre-treatment are accurately weighed in the tool plug centrifuge tube of 50mL.
The pre-treatment of 2 samples:
30mL methanol is added into the above-mentioned centrifuge tube for having claimed sample, is vortexed to mix and is extracted 3mim, lead acetate solid is added
N-hexane 20mL is added in 2.00g, vortex 1min, vibrates 15min, and revolving speed 2500r/min is centrifuged 3min, collects whole supernatants
Liquid, the rotary evaporated to dryness at 50 DEG C, be added 2.00mL dimethylbenzene constant volume, cross 0.45 μm of filter membrane after it is to be analyzed.
3 chromatography-mass spectroscopy testing conditions:
3.1 chromatographic columns: DB-5MS capillary column, 30m × 0.25mm (internal diameter), 0.25 μm.
3.2 temperature programs: 60 DEG C of holding 1min are warming up to 200 DEG C with 12 DEG C/min rate, keep 7min.
3.3 injector temperatures: 280 DEG C.
3.4 chromatographic mass spectrometry interface temperatures: 280 DEG C.
3.5 ionization modes: EI (70ev).
3.6 ion source temperatures: 230 DEG C.
3.7 carrier gas: helium, purity are greater than 99.999%, flow velocity 1.0mL/min.
3.8 input modes: it does not shunt；
3.9 sample volumes: 1 μ L.
3.10 mensuration modes: Salbutamol Selected Ion Monitoring (SIM).
3.11 selection monitorings ion (m/z): 120.1,107.1,157.1,251.2 (abundance ratio are as follows: 100-74-54-20)；
3.12 solvent delays: 10min.
4 sample detections and confirmation
The preparation of 4.1 standard working curves:
Suitable OK a karaoke club aldehyde standard substance is taken, 50.0mL is settled to acetone and is configured to 1000mg/L standard reserving solution,
It is saved backup in -4 DEG C of refrigerators.
Pipette respectively the standard reserving solution of 1000mg/L with acetone soln be diluted to concentration for 1mg/L, 2mg/L, 10mg/L,
The karanal standard working solution of 20mg/L, 100mg/L.1 μ L injection gas chromatograph-mass spectrometer is accurately drawn respectively to be divided
Analysis, is tested according to above-mentioned chromatography-mass spectroscopy testing conditions (step 3).Using the concentration of standard substance as abscissa, peak area
Standard working curve is drawn for ordinate.
4.2 qualitatively and quantitatively analyze
According to measured object content situation in final analysis prepare liquid, the standard working solution of concentration comparable is selected, to standard
Working solution and sample liquid are joined in equal volume injects sample measurement, the measurement of karanal content in standard specimen working solution and the sample solution to be tested
Response should all be in the range of linearity that instrument detects.
If in sample liquid and the selection chromatography of ions figure of standard working solution, had in identical retention time (± 0.05min)
Chromatographic peak occurs, and in the sample mass spectrum after background correction, selected ion occurs, the abundance ratio of selected ion with
Standard items correspond to the abundance ratio of ion, and value within the allowable range, is shown in Table 1.External standard method is carried out according to quota ion pair object
It is quantitative.4.3 blank assay
In addition to not weighing sample, remaining presses pre-treatment step progress.
The calculating and statement of 5 testing results:
Object residual quantity in sample is calculated with chromatographic data processor or by formula (1):
In formula:
X --- the residual quantity of object in sample, unit are milligrams per kilogram (mg/kg)；
S --- the chromatographic peak area of object in sample liquid；
Ss--- the chromatographic peak area of object in standard working solution；
C --- the concentration of object in standard working solution, unit are micrograms per millilitre (μ g/mL)；
V --- the final constant volume of sample liquid, unit are milliliter (mL)；
M --- sample mass representated by final sample liquid, unit are gram (g)；
The range of linearity, linear equation, related coefficient, detection limit and the quantitative limit of 6 measurement cleaning solution samples are shown in Table 4；
Linear equation, related coefficient, the range of linearity, detection limit and the quantitative limit of karanal in 4 cleaning solution of table
7 in the case where 1,2 and 10mg/kg, tri- spiked levels are horizontal, and the rate of recovery and precision that each horizontal checkout is six times are such as
Shown in table 5:
The recovery of standard addition of karanal and precision (n=6) in 5 cleaning solution of table
The clean-up effect comparison diagram of mark-on cleaning solution and positive cleaning solution is shown in 8 Fig. 3.
Embodiments of the present invention above described embodiment only expresses, the description thereof is more specific and detailed, but can not
Therefore limitations on the scope of the patent of the present invention are interpreted as.It should be pointed out that for the ordinary skill in the art,
Without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to protection model of the invention
It encloses, therefore the scope of protection of the patent of the invention shall be subject to the appended claims.
Claims (4)
1. the detection method of karanal in a kind of articles for washing, the pre-treatment of preparation, sample including sample, sample detection are true
The calculating and statement of card and testing result, it is characterised in that:
(1) it the extraction for solid-state and semisolid sample: is added into the tool plug centrifuge tube for having weighed 1.000~2.000g sample
20~30mL acetonitrile is vortexed, and lead acetate solid is added in ultrasonic extraction, is vortexed, and n-hexane is added, and vibrates, and centrifugation is collected all
Supernatant, rotary evaporated to dryness, constant volume are to be analyzed after membrane filtration；
(2) for the extraction of liquid sample: adding 20~30mL second into the centrifuge tube for having weighed 1.000~2.000g sample
Nitrile, is vortexed to mix and extract, lead acetate solid is added, is vortexed, n-hexane is added, vibrates, and whole supernatants, rotation are collected in centrifugation
It is evaporated to dryness, constant volume, it is to be analyzed after membrane filtration；
(3) chromatography-mass spectroscopy testing conditions: chromatographic column: DB-5MS capillary column, length × internal diameter are 30m × 0.25mm, and film thickness is
0.25μm；Temperature program: 60 DEG C of holding 1min are warming up to 200 DEG C with 12 DEG C/min rate, keep 7min；Injector temperature:
280℃；Chromatographic mass spectrometry interface temperature: 280 DEG C；Ionization mode: the source EI, ionization voltage 70ev；Ion source temperature: 230 DEG C；It carries
Gas: helium, purity are greater than 99.999%, flow velocity 1.0mL/min；Input mode: it does not shunt；Sample volume: 1 μ L；Mensuration mode: choosing
Select ion monitoring；Select monitoring ion m/z be 120.1,107.1,157.1,251.2；Selection monitoring abundance of ions ratio are as follows: 100:
74:54:20；Solvent delay: 10min.
2. the detection method of karanal in articles for washing according to claim 1, which is characterized in that the lead acetate
Dosage be 1.0~2.0g, n-hexane dosage be 10~15mL.
3. the detection method of karanal in articles for washing according to claim 1, which is characterized in that the constant volume liquid
For acetone, toluene or dimethylbenzene, dosage 2.00mL.
4. the detection method of karanal in articles for washing according to claim 1, which is characterized in that the ultrasound mentions
20~30min of time is taken, centrifugal rotational speed is 2500~4500r/min, and 3~5min of centrifugation time, vortex time is 1~3min,
Duration of oscillation is 15~30min, and rotating evaporation temperature is 40~50 DEG C, and filtering membrane aperture is 0.22~0.45 μm.
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|---|---|---|---|---|
| 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 |
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Patent Citations (3)
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|---|---|---|---|---|
| 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 |
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