CN108051518B - Automatic detection method for benzophenone and 4-methylbenzophenone in electronic cigarette liquid - Google Patents
Automatic detection method for benzophenone and 4-methylbenzophenone in electronic cigarette liquid Download PDFInfo
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- CN108051518B CN108051518B CN201711277123.XA CN201711277123A CN108051518B CN 108051518 B CN108051518 B CN 108051518B CN 201711277123 A CN201711277123 A CN 201711277123A CN 108051518 B CN108051518 B CN 108051518B
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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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
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Abstract
An automatic detection method for benzophenone and 4-methylbenzophenone in electronic cigarette liquid is characterized in that pretreatment automation of an electronic cigarette sample is combined with online gas chromatography-mass spectrometry for detection, namely, the electronic cigarette liquid sample is directly placed in a chromatographic bottle, then the adding amount of water, dichloromethane and an internal standard is set, an instrument is automatically added, the instrument is swirled, and a lower dichloromethane phase is taken out to enter a gas chromatography-mass spectrometer for detection on line. Compared with the existing detection method, the invention has the following technical advantages: 1. the whole process of sample pretreatment and sample introduction is automatically operated, so that the difference and the accuracy error in the manual sample treatment are reduced, the repeatability is high, and the general survey analysis result is reliable; the consumption of solvent and the sample amount are less, and the environment is protected; the method is rapid and efficient, is suitable for the general investigation and analysis of a large amount of samples, and can process and analyze 150 samples at a time. 2. The method avoids inaccurate measuring result of the target object caused by solvent volatilization before conventional off-line detection, and the sample is introduced immediately after each sample is pretreated, so that the measuring result is accurate and reliable.
Description
Technical Field
The invention belongs to the technical field of electronic cigarette liquid determination, and particularly relates to an automatic detection method for benzophenone and 4-methylbenzophenone in electronic cigarette liquid. The method has the advantages that the pretreatment of the electronic cigarette liquid is automated and is combined with online gas chromatography-mass spectrometry detection, the used solvent for pretreatment is less, the whole process is automated, and the accuracy and the repeatability are good.
Background
An electronic cigarette (e-cigarette), also known as an Electronic Nicotine Delivery System (ENDS), is an electronic device that delivers nicotine to the respiratory system by electronic heating means, and is a new way of smoking nicotine. The electronic cigarette liquid mainly comprises nicotine, propylene glycol, glycerol or polyethylene glycol, and a small amount of essence can be added to prepare different tastes to meet the requirements and hobbies of consumers.
Benzophenone and 4-methylbenzophenone are intermediates of organic pigments, medicines, perfumes and pesticides, and have irritation, and the European Union (EC) No 19/2007 regulation stipulates that the migration amounts of 4-methylbenzophenone and benzophenone in food packaging materials cannot exceed 0.6 mu g/g in total, but electronic cigarette products lack supervision and have irregular quality, and the content of benzophenone and 4-methylbenzophenone in some electronic cigarette liquid is over-determined.
At present, the analysis method of benzophenone and 4-methylbenzophenone in the literature focuses on the detection of instrument analysis, and few pretreatment researches are carried out, and the pretreatment of benzophenone and 4-methylbenzophenone is mostly carried out by manual off-line treatment, namely, a solvent is added into a sample for extraction, an extract is taken to be subjected to instrument analysis, but the manual pretreatment is not suitable for general investigation analysis of a large number of samples, and the deviation caused by pretreatment human factors is large, the system error is large, and the precision is poor; when a large number of samples are analyzed, long-time waiting time is generated before sample introduction, the concentration of a target substance is changed due to the fact that the solvent is volatile, and the measuring result is inaccurate.
Disclosure of Invention
The invention aims to provide an automatic detection method of benzophenone and 4-methylbenzophenone in electronic cigarette liquid, which aims at the existing situation, the method is based on an integrated sample preparation workbench and a gas chromatography-mass spectrometry detector to build a platform and set a program, the sample pretreatment is automatically operated, the online gas chromatography-mass spectrometry detection is realized, the high accuracy and repeatability of the result can be realized, the log recording and resource tracking functions are provided, the result tracing search is convenient, the used solvent in the whole process is less, and the labor cost is greatly saved.
The purpose of the invention is realized by the following scheme: an automatic detection method for benzophenone and 4-methylbenzophenone in electronic cigarette liquid is characterized in that the detection is carried out through the combination of the pretreatment automation of an electronic cigarette liquid sample and the online gas chromatography-mass spectrometry, namely the electronic cigarette liquid sample is weighed and directly placed in a chromatographic bottle of a chromatograph, then the adding amount of water, dichloromethane and an internal standard is set through an operating panel of the chromatograph, so that an instrument is automatically added, a lower dichloromethane phase is taken out and enters a gas chromatography-mass spectrometer online for detection, and the specific detection steps are as follows:
(1) pre-treating a sample, namely taking 0.01-1 m L electronic cigarette liquid into a chromatographic bottle, directly adding 0.1-1 m L of water and 0.1-5 m L of dichloromethane and 4-fluorobenzophenone internal standard through setting, and taking a dichloromethane phase 1 mu L at the lower layer for GC-MS detection after swirling for 1-10 min;
(2) and (3) preparing a standard working solution, namely setting and preparing a mixed solution with five gradient concentrations, wherein the internal standard concentration of the standard solution is 1 mu g/m L, and the concentration of benzophenone and 4-methylbenzophenone is 0.1-10 mu g/m L, through an operation panel.
(3) Analysis of the samples:
GC-MS analysis conditions:
the method comprises the following steps of sampling port temperature 270 ℃, sampling amount 1 mu L, split ratio 10:1, carrier gas helium, constant flow rate 1m L/min, chromatographic column DB-5MS, specification 30m × 0.25mm × 0.25.25 mu m, programmed temperature rise, starting temperature 100 ℃, keeping for 2min, raising to 300 ℃ at the speed of 20 ℃/min, and keeping for 5 min;
an ionization mode: EI; transmission line temperature: 280 ℃; ion source temperature: 230 ℃;
the scanning mode is as follows: SIM, benzophenone with 105 quantitative ions and 51, 182 qualitative ions; the quantitative ion of 4-methylbenzophenone is 119, and the qualitative ion is 91, 196; the quantitative ion of 4-fluorobenzophenone (internal standard) is 123, the qualitative ion is 95, 200, and the monitoring time for each ion is 50 ms;
(4) drawing a standard curve and calculating a result: performing area integration on the response of the series of standard solutions, making a correction curve according to the ratio of the response area ratio of the benzophenone, the 4-methylbenzophenone and the internal standard to the content, and fitting by using a straight line to obtain a unitary linear regression equation; and (3) measuring the prepared sample, measuring the peak area ratio of the benzophenone and the 4-methylbenzophenone to the internal standard in the sample, substituting the peak area ratio into a unitary linear regression equation, and calculating to obtain the content of the benzophenone and the 4-methylbenzophenone.
And (2) the lower-layer dichloromethane phase in the step (1) is realized by setting the depth of a sample injection needle, namely the sample injection needle is 2 mm away from the bottom of the chromatographic bottle.
The sample preparation station may be comprised of a double column injector and a sample tray with a vortex function.
The sample tray is 150, 150 electronic cigarette liquid samples can be processed at one time, the sample processing method is the same, and only the sequence name and the result name are different.
The water used is high purity water.
A certain electronic cigarette liquid sample is added with benzophenone and 4-methylbenzophenone standard solutions with high, medium and low content levels to perform a recovery rate experiment, the in-day repeatability and the in-day repeatability of the method are measured, the Relative Standard Deviation (RSD) of the measured result is used for representing that the recovery rate is 95.1% -100.5%, the in-day precision is 0.3% -1.2%, and the in-day precision is 0.5% -1.6%, so that the method is good in recovery rate and repeatability and high in practical application value.
Compared with the existing detection method, the method has the following technical advantages:
1. the whole process of sample pretreatment and sample introduction is automatically operated, so that the difference and the accuracy error in the manual sample treatment are greatly reduced, the repeatability is high, and the general survey analysis result of the sample is reliable; the consumption of solvent and the sample amount are less, and the environment is protected; the method is rapid and efficient, is suitable for the general investigation and analysis of a large batch of samples, and can process and analyze 150 samples at one time.
2. The electronic cigarette liquid has various brands and tastes, the quantity of samples for general investigation and analysis is large, the result is accurate and reliable, and the pretreatment of the benzophenone and the 4-methylbenzophenone does not need concentration and manual intervention, so that the method is suitable for the pretreatment of a large number of samples.
3. By adopting conventional off-line detection, the processed sample can be placed in a sample tray for a long time before the sample is injected by the instrument, and the dichloromethane solvent is volatile, so that the concentration of a target substance is changed, and the measurement result is inaccurate. The sample pretreatment automation of the invention is combined with the gas chromatography-mass spectrometer on-line detection, so that each sample can be immediately injected after pretreatment, long-time instrument waiting is avoided, and the measurement result is accurate and reliable.
Drawings
FIG. 1: and the content of the benzophenone and the 4-methylbenzophenone is 0.8 mu g/g of the electronic cigarette liquid chromatogram. In the figure: 1 is benzophenone, 2 is internal standard 4-fluorobenzophenone, and 3 is 4-methylbenzophenone.
Detailed Description
The invention is further illustrated by the following examples:
example 1
1. The pretreatment of a sample to be detected is that about 500 mu L electronic cigarette liquid is added into a sample tray chromatographic bottle, 0.5 m L of water is added into the sample through a front sample injection tower, 0.5 m L of dichloromethane is added into the sample through setting in sequence, 4-fluorobenzophenone internal standard 50 u L is added into the sample through a rear sample injection tower, the sample is mixed for 1 min at 1500 RPM, the waiting time is 5 min, the sample bottle is moved to a front sample injection tower, and a dichloromethane phase 1 mu L at the lower layer is taken out and subjected to GC-MS detection.
2. The GC-MS analysis conditions comprise a sample inlet temperature of 270 ℃, a sample feeding amount of 1 mu L, a split flow ratio of 10:1, a carrier gas of helium at a constant flow rate of 1m L/min, a chromatographic column of DB-5MS with a specification of 30m × 0.25mm × 0.25.25 mu m, a programmed temperature rise of 100 ℃, a starting temperature of 2min, a temperature rise rate of 20 ℃/min to 230 ℃, an ionization mode of 5 min, an transmission line temperature of 280 ℃, an ion source temperature of 230 ℃, a scanning mode of SIM, a quantitative ion of benzophenone of 105, a qualitative ion of 51, 182, a quantitative ion of 4-methylbenzophenone of 119, a qualitative ion of 91, 196, a quantitative ion of 4-fluorobenzophenone of 123, a qualitative ion of 95, 200 and a monitoring time of 50MS for each ion.
3. The preparation of standard working solution comprises placing 5 empty chromatographic bottles in a sample tray, respectively adding 1m L dichloromethane into a first empty chromatographic bottle by arranging an advancing sample tower, respectively adding 1 mu L as an internal standard of 4-fluorobenzophenone into the first empty chromatographic bottle by an advancing sample tower, adding 0.1 mu L0 of benzophenone into the first empty chromatographic bottle by a rear sample tower, adding 0.1 mu L of 4-methylbenzophenone into the empty chromatographic bottle by the rear sample tower, mixing the empty chromatographic bottles at 1500 RPM for 1 min, waiting for 1 min, moving the empty chromatographic bottles to the advancing sample tower, taking 1 mu L, and sequentially carrying out GC-MS detection and standard solution preparation, wherein after the first chromatographic bottle is prepared, the next chromatographic bottle is prepared and injected, the adding amount of the solvent and the internal standard in the remaining four chromatographic bottles is consistent with that of the first chromatographic bottle, the adding amount of the benzophenone and the 4-methylbenzophenone are respectively 1 mu L, 3 mu L, 6 mu L and 10 mu L, the concentration of the internal standard solution is 1 mu g/m, the concentration of the internal standard solution is L g/m, and the concentration of the mixed solution is equal to that of the five methyl benzophenone, 3 mu L and the mixed solution is 1-L.
4. Drawing a standard curve and calculating a result: area integration of responses from series of standard solutions with benzophenone, 4-methylbenzophenone and an internal standardThe ratio of the response area to the content is used as a correction curve, and a straight line is used for fitting to obtain a unitary linear regression equation and a correlation coefficient R2Should not be less than 0.999. And (3) measuring the prepared sample, measuring the peak area ratio of the benzophenone, the 4-methylbenzophenone and the internal standard in the sample, substituting the peak area ratio into a unitary linear regression equation, and calculating to obtain the content of the benzophenone and the 4-methylbenzophenone.
According to the automatic detection method for benzophenone and 4-methylbenzophenone in the electronic cigarette liquid, the pretreatment and detection time of each electronic cigarette liquid sample is not more than 20min, 36 hours are required for the general investigation of 120 electronic cigarette liquids, and compared with the offline manual pretreatment requiring 5 working days, the time is greatly saved, and the working efficiency is improved; the precision of the monitored sample is within 2 percent and is much lower than the precision of 10 percent of the offline manual pretreatment; in total 11 of 120 samples, the benzophenone and the 4-methylbenzophenone are detected, and the detected amount is 0.3-5 mu g/g, so that the general investigation and supervision of the benzophenone and the 4-methylbenzophenone in the electronic cigarette liquid are necessary.
Claims (3)
1. An automatic detection method of benzophenone and 4-methylbenzophenone in electronic cigarette liquid is characterized by comprising the following steps: the method is based on an integrated sample preparation workbench and a gas chromatography-mass spectrometry detector to build a platform and set programs, the sample pretreatment automation operation is realized, and the online gas chromatography-mass spectrometry detection is realized, namely, an electronic cigarette liquid sample is directly placed in a chromatographic bottle of a chromatograph, then the adding amount of water, dichloromethane and internal standards is set through a chromatograph operation panel, so that the instrument is automatically added, vortexed, a lower dichloromethane phase is taken out to be detected in the online gas chromatography-mass spectrometer, the sample preparation workbench is composed of a double-tower sample injector and a sample disc with a vortexing function, and the specific determination steps are as follows:
(1) the sample pretreatment comprises the steps of putting 0.01-1 m L electronic cigarette liquid into a chromatographic bottle, directly adding 0.1-1 m L water and 0.1-5 m L dichloromethane and 4-fluorobenzophenone internal standard by setting, carrying out vortex for 1-10 min, and taking a lower dichloromethane phase 1 mu L for GC-MS detection, wherein the taking of the lower dichloromethane phase is realized by setting the depth of a sample injection needle, namely the sample injection needle is 2 mm from the bottom of the chromatographic bottle;
(2) preparation of standard working solutions: preparing a dichloromethane solution of benzophenone and 4-methylbenzophenone with five concentration gradients of 0.5-10 mu g/g and an internal standard of 4-fluorobenzophenone of 1 mu g/g as a mixed standard working solution;
(3) analysis of the samples:
GC-MS analysis conditions:
the method comprises the following steps of sampling port temperature 270 ℃, sampling amount 1 mu L, split ratio 10:1, carrier gas helium, constant flow rate 1m L/min, chromatographic column DB-5MS, specification 30m × 0.25mm × 0.25.25 mu m, programmed temperature rise, starting temperature 100 ℃, keeping for 2min, raising to 300 ℃ at the speed of 20 ℃/min, and keeping for 5 min;
an ionization mode: EI; transmission line temperature: 280 ℃; ion source temperature: 230 ℃;
the scanning mode is as follows: SIM, benzophenone with 105 quantitative ions and 51, 182 qualitative ions; the quantitative ion of 4-methylbenzophenone is 119, and the qualitative ion is 91, 196; the quantitative ion of the 4-fluorobenzophenone is 123, the qualitative ion of the 4-fluorobenzophenone is 95, 200, and the monitoring time of each ion is 50 ms;
(4) drawing a standard curve and calculating a result: performing area integration on the response of the series of standard solutions, making a correction curve according to the ratio of the response area ratio of the benzophenone, the 4-methylbenzophenone and the internal standard to the content, and fitting by using a straight line to obtain a unitary linear regression equation; and (3) measuring the prepared sample, measuring the peak area ratio of the benzophenone and the 4-methylbenzophenone to the internal standard in the sample, substituting the peak area ratio into a unitary linear regression equation, and calculating to obtain the content of the benzophenone and the 4-methylbenzophenone.
2. The automated detection method of claim 1, wherein: the sample tray is 150, can handle 150 electron tobacco juice samples once.
3. The automated detection method of claim 1, wherein: the water used is high purity water.
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| CN102235949A (en) * | 2010-04-30 | 2011-11-09 | 中国科学院大连化学物理研究所 | Gas phase-liquid phase on-line combined dioxin sample purification device |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102235949A (en) * | 2010-04-30 | 2011-11-09 | 中国科学院大连化学物理研究所 | Gas phase-liquid phase on-line combined dioxin sample purification device |
| CN102818874A (en) * | 2012-08-31 | 2012-12-12 | 国家烟草质量监督检验中心 | Detection method of determining 16 types of photoinitiators in paper printing and packaging material |
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| Analysis of benzophenone and 4-methylbenzophenone in breakfast cereals using ultrasonic extraction in combination with gas chromatography-tandem mass spectrometry (GC-MSn);Van Hoeck, E 等;《ANALYTICA CHIMICA ACTA》;20100331;第663卷(第1期);第55-59页 * |
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