CN108051518A - The automated detection method of benzophenone and 4- methyl benzophenones in a kind of electronic cigarette liquid - Google Patents
The automated detection method of benzophenone and 4- methyl benzophenones in a kind of electronic cigarette liquid Download PDFInfo
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- CN108051518A CN108051518A CN201711277123.XA CN201711277123A CN108051518A CN 108051518 A CN108051518 A CN 108051518A CN 201711277123 A CN201711277123 A CN 201711277123A CN 108051518 A CN108051518 A CN 108051518A
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- benzophenone
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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
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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
Abstract
The automated detection method of benzophenone and 4 methyl benzophenones in a kind of electronic cigarette liquid, it is to automate to be detected with reference to online gaschromatographic mass spectrometry by electronic cigarette sample pre-treatments, electronic cigarette liquid sample is placed directly in chromatogram bottle, water, dichloromethane, interior target addition are set afterwards, it is automatically added to instrument, it is vortexed, removes layer dichloromethane mutually online into detecting in gas chromatography mass spectrometer.It is of the invention compared with existing detection method, technical advantage is as follows：1st, sample pre-treatments and the operation of sample introduction whole-course automation, difference and accuracy errors when reducing artificial treatment sample, repeatability is high, Analysis of check-up reliable results；It consumes solvent and sample size is few, it is more environmentally friendly；Quickly, efficiently, suitable for batch samples Analysis of check-up, 150 samples of analysis can once be handled.2nd, before avoiding Conventional Off-line detection, object measurement result caused by solvent volatilization is inaccurate, and sample introduction immediately after each sample pre-treatments, measurement result is accurately and reliably.
Description
Technical field
The invention belongs to electronic cigarette liquid determination techniques fields, and in particular to benzophenone and 4- methyl in a kind of electronic cigarette liquid
The automated detection method of benzophenone.This method electronic cigarette liquid pre-treatment automates and combines online gas chromatography-mass spectrum inspection
It surveys, pre-treatment is few using solvent, whole-course automation operation, accuracy, reproducible.
Background technology
Electronic cigarette（electrical cigarette, e-cigarette）, also known as electronics nicotine transmission system
（electronic nicotine delivery systems, ENDS）, be it is a kind of by electronics heater means to respiratory system
The electronic device of nicotine is transmitted, is a kind of new paragon for sucking nicotine.Tobacco juice for electronic smoke mainly by nicotine, propylene glycol, glycerine or
Polyethylene glycol is formed, and in addition can be added a small amount of essence, be made different tastes to cater to consumer demand and hobby.
Benzophenone and 4- methyl benzophenones are the intermediates of organic pigment, medicine, fragrance, insecticide, and having stimulates
Property, 4- methyl benzophenones and benzophenone the amount of migration are total in 19/2007 rules and regulations packaging materials for food of European Union (EC) No
Altogether no more than 0.6 μ g/g, but electronics smoke product lacks supervision, and quality is irregular, and hexichol is detected in some electronic cigarette liquids
Ketone and 4- methyl benzophenone contents are exceeded.
At present, the analysis method of benzophenone and 4- methyl benzophenones focuses on the detection of Instrumental Analysis in document, right
Pre-treatment is studied less, and the pre-treatment of benzophenone and 4- methyl benzophenones is mostly artificial processed offline, i.e., in the sample
Solvent extraction is added in, takes extract liquor into Instrumental Analysis, but manually pre-treatment does not apply to the Analysis of check-up with batch samples, before
The deviation that processing human factor introduces is big, and systematic error is big, and precision is poor；When gross sample is analyzed, had before sample introduction for a long time
Stand-by period, and solvent is volatile that target concentration can be caused to change, and measurement result is inaccurate.
The content of the invention
The purpose of the present invention is benzophenone and 4- methyl in a kind of electronic cigarette liquid for being directed to more than current condition and providing
The automated detection method of benzophenone, this method rely on integrated preparation of samples workbench and gas chromatography-mass spectrum detector
It sets for this platform and setting program, sample pre-treatments automation mechanized operation and realizes online gas chromatography-mass spectrum detection, it can be achieved that result
High accuracy and repeatability, and provide log recording and resource tracing function, result facilitated to trace to the source lookup, and whole process makes
Few with solvent, human cost also greatlys save.
The purpose of the present invention is what is realized by following scheme：Benzophenone and 4- methyldiphenyls in a kind of electronic cigarette liquid
The automated detection method of ketone is to automate to combine the progress of online gas chromatography-mass spectrum by electronic cigarette liquid sample pre-treatments
Detection, that is, weigh electronic cigarette liquid sample be placed directly in chromatographic chromatogram bottle, afterwards by chromatograph operation panel set water,
Dichloromethane, interior target addition, are automatically added to instrument, remove layer dichloromethane mutually online into gas chromatograph-mass spectrometer
Detection, specific determination step are as follows：
(1) sample pre-treatments：0.01~1mL electronic cigarette liquids are taken in chromatogram bottle, 0.1~1 mL water is directly added by setting
With 0.1~5 mL dichloromethane and 4- fluorine benzophenone internal standards, be vortexed 1~10 min after, remove 1 μ L of layer dichloromethane phase into
GC-MS is detected；
(2) preparation of standard working solution：Preparing standard solution internal standard concentration is set as 1 μ g/mL, hexichol by operation panel
Ketone and 4- methyl benzophenones concentration are the mixed solution of five gradient concentrations of 0.1~10 μ g/ mL.
(3) analysis of sample：
GC-MS analysis conditions：
Injector temperature：270℃；Sample size：1µL；Split ratio 10:1；Carrier gas：Helium, constant current flow velocity 1mL/min；Chromatographic column：
DB-5MS, specification 30m × 0.25mm × 0.25 μm；Temperature programming：100 DEG C of initial temperature keeps 2min, with 20 DEG C/min's
Rate rises to 300 DEG C, keeps 5 min；
Ionization mode：EI；Transmission line temperature：280℃；Ion source temperature：230℃；
Scan mode：SIM, the quota ion of benzophenone is 105, and qualitative ion is 51,182；4- methyl benzophenones are determined
It is 119 to measure ion, and qualitative ion is 91,196；4- fluorine benzophenone（Internal standard）Quota ion for 123, qualitative ion is 95,
200, the monitoring time to each ion is 50ms；
(4) Specification Curve of Increasing and result calculate：Area integral is carried out to the response of series standard solution, with benzophenone and 4-
Methyl benzophenone and interior target response surface product compare the ratio between content and do calibration curve, are fitted with straight line, it is linear to obtain unitary
Regression equation；The sample of preparation is measured, measures benzophenone in sample and 4- methyl benzophenones and internal standard peak face
Product ratio, brings unary linear regression equation into, benzophenone and 4- methyl benzophenone contents is calculated.
Step（1）In remove layer dichloromethane mutually by the way that sample introduction needle depth is set to realize, i.e., sample introduction needle is away from chromatography
2 ㎜ of bottom of bottle portion.
Preparation of samples workbench can be made of double tower injector and the sample disc with vortex.
Sample disc is 150, can once handle 150 electronic cigarette liquid samples, sample treatment is identical, only sequence names
And result name is different.
The water used is high purity water.
A certain tobacco juice for electronic smoke sample is added to the benzophenone and 4- methyldiphenyl first of high, medium and low three contents levels
Ketone standard solution does rate of recovery experiment, is carried out at the same time the in a few days repeated of this method and repeatability measures in the daytime, use measurement result
Relative standard deviation（RSD）It represents, the rate of recovery is between 95.1%-100.5%, and withinday precision is between 0.3%-1.2%, day
Between precision between 0.5%-1.6%, illustrate this method rate of recovery and reproducible, actual application value is high.
It is of the invention compared with existing detection method, have following technical advantage：
1st, sample pre-treatments and the operation of sample introduction whole-course automation, difference and accuracy when substantially reducing artificial treatment sample are missed
Difference has high repeatability, the Analysis of check-up reliable results of sample；It consumes solvent and sample size is few, it is more environmentally friendly；Quickly, efficiently,
Suitable for the Analysis of check-up of batch samples, it can once handle and analyze 150 samples.
2nd, electronic cigarette liquid brand and taste are numerous, and Analysis of check-up sample size is big, and to ensure result accurately and reliably, due to two
The pre-treatment of Benzophenone and 4- methyl benzophenones is without concentration and manual intervention, suitable for gross sample pre-treatment.
3rd, using conventional offline inspection, treated when sample can place very long before instrument sample introduction in sample disc
Between, and dichloromethane solvent is volatile, and target concentration can be caused to change, so as to which measurement result is inaccurate.It is and of the invention
Sample pre-treatments automation in combination with gas chromatograph-mass spectrometer on-line checking, can make after each sample pre-treatments immediately into
Sample avoids prolonged instrument from waiting, and measurement result is accurately and reliably.
Description of the drawings
Fig. 1：Benzophenone and the electronic cigarette liquid chromatography that 4- methyl benzophenones content is 0.8 μ g/g.In figure：1 is two
Benzophenone, 2 be internal standard 4- fluorine benzophenone, and 3 be 4- methyl benzophenones.
Specific embodiment
The present invention is further described below by embodiment：
Embodiment 1
1st, the pre-treatment of sample to be tested：About 500 μ L electronic cigarette liquids are added in sample disc chromatogram bottle, before making successively by setting
0.5 mL water is added to sample by sample introduction tower；0.5 mL dichloromethane is added to sample；Sample introduction tower will be in 4- fluorine benzophenone afterwards
It marks 50 uL and is added to sample；Sample is mixed into 1 min with 1500 RPM speed；Wait 5 min；Sample bottle is moved to advance
Sample tower；1 μ L of layer dichloromethane phase are removed to detect into GC-MS.
2nd, GC-MS analysis conditions：Injector temperature：270℃；Sample size：1µL；Split ratio 10:1；Carrier gas：Helium, constant current
Flow velocity 1mL/min；Chromatographic column：DB-5MS, specification 30m × 0.25mm × 0.25 μm；Temperature programming：100 DEG C of initial temperature is kept
2min rises to 230 DEG C with the rate of 20 DEG C/min, keeps 5 min.Ionization mode：EI；Transmission line temperature：280℃；Ion source
Temperature：230℃.Scan mode：SIM, the quota ion of benzophenone is 105, and qualitative ion is 51,182；4- methyldiphenyls
The quota ion of ketone is 119, and qualitative ion is 91,196；The quota ion of 4- fluorine benzophenone is 123, and qualitative ion is
95,200, the monitoring time to each ion is 50ms.
3rd, the preparation of standard working solution：5 empty chromatogram bottles are placed in sample disc, distinguish preceding sample introduction tower by setting
1 mL dichloromethane is added in first empty chromatogram bottle；1 μ L of 4- fluorine benzophenone internal standard are added to first by sample introduction tower afterwards
A sky chromatogram bottle；0.1 μ L of benzophenone are added to first empty chromatogram bottle by sample introduction tower afterwards；Sample introduction tower is by 4- methyldiphenyl first afterwards
0.1 μ L of ketone are added to sky chromatogram bottle；Empty chromatogram bottle is mixed into 1 min with 1500 RPM speed；Wait 1 min；By empty chromatogram bottle
Sample introduction tower before being moved to；1 μ L is taken to be detected into GC-MS.Standard solution preparation carries out successively, prepares and finishes in first chromatogram bottle
After sample introduction, next chromatogram bottle prepares sample introduction again, and solvent and internal standard addition are consistent with first in remaining four chromatogram bottles, and two
Benzophenone and 4- methyl benzophenone additions are respectively 1 μ L, 3 μ L, 6 μ L, 10 μ L.Standard solution internal standard concentration is 1 μ g/mL,
Benzophenone and 4- methyl benzophenones concentration are the mixed solution of five gradients of 0.1,1,3,6,10 μ g/ mL.
4th, Specification Curve of Increasing and result calculate：Area integral is carried out to the response of series standard solution, with benzophenone,
4- methyl benzophenones and interior target response surface product compare the ratio between content and do calibration curve, are fitted with straight line, obtain unitary line
Property regression equation, coefficient R20.999 should be not less than.The sample of preparation is measured, measure benzophenone in sample,
4- methyl benzophenones and internal standard peak area ratio, bring unary linear regression equation into, benzophenone, 4- methyldiphenyls are calculated
Ketone content.
According to the automated detection method of benzophenone and 4- methyl benzophenones in a kind of foregoing electronic cigarette liquid,
Each electronic cigarette liquid sample pre-treatments and detection time are no more than 20min, generally investigate 120 electronic cigarette liquids, need 36 hours altogether, than
Offline manually pre-treatment needs 5 working days to compare, and the time is greatly saved, improves work efficiency；Monitoring sample precision exists
It is more much smaller than offline manually pre-treatment precision 10% within 2%；11, which are shared, in 120 samples has detected benzophenone and 4-
Methyl benzophenone, between 0.3~5 μ g/g of detected level, therefore, benzophenone and 4- methyl benzophenones is general in electronic cigarette liquid
Supervision is looked into be necessary.
Claims (5)
1. a kind of automated detection method of benzophenone and 4- methyl benzophenones in electronic cigarette liquid, it is characterised in that：The party
Method relies on integrated preparation of samples workbench and gas chromatography-mass spectrum detector is set for this platform and setting program, sample pre-treatments
Automation mechanized operation and the online gas chromatography-mass spectrum detection of realization, i.e., be placed directly within chromatographic chromatogram bottle by electronic cigarette liquid sample
In, water, dichloromethane, interior target addition are set by chromatograph operation panel afterwards, are automatically added to instrument, is vortexed, takes
Mutually online into detecting in gas chromatograph-mass spectrometer, specific determination step is as follows for lower floor dichloromethane：
(1) sample pre-treatments：0.01~1mL electronic cigarette liquids are taken in chromatogram bottle, 0.1~1 mL water is directly added by setting
With 0.1~5 mL dichloromethane and 4- fluorine benzophenone internal standards, be vortexed 1~10 min after, remove 1 μ L of layer dichloromethane phase into
GC-MS is detected；
(2) preparation of standard working solution：Prepare benzophenone and 4- with 0.5 μ g/g~10 μ g/g, five concentration gradients
The dichloromethane solution of 1 μ g/g of methyl benzophenone and internal standard 4- fluorine benzophenone is as hybrid standard working solution；
(3) analysis of sample：
GC-MS analysis conditions：
Injector temperature：270℃；Sample size：1µL；Split ratio 10:1；Carrier gas：Helium, constant current flow velocity 1mL/min；Chromatographic column：
DB-5MS, specification 30m × 0.25mm × 0.25 μm；Temperature programming：100 DEG C of initial temperature keeps 2min, with 20 DEG C/min's
Rate rises to 300 DEG C, keeps 5 min；
Ionization mode：EI；Transmission line temperature：280℃；Ion source temperature：230℃；
Scan mode：SIM, the quota ion of benzophenone is 105, and qualitative ion is 51,182；4- methyl benzophenones are determined
It is 119 to measure ion, and qualitative ion is 91,196；The quota ion of 4- fluorine benzophenone is 123, and qualitative ion is 95,200, right
The monitoring time of each ion is 50ms；
(4) Specification Curve of Increasing and result calculate：Area integral is carried out to the response of series standard solution, with benzophenone and 4-
Methyl benzophenone and interior target response surface product compare the ratio between content and do calibration curve, are fitted with straight line, it is linear to obtain unitary
Regression equation；The sample of preparation is measured, measures benzophenone in sample and 4- methyl benzophenones and internal standard peak face
Product ratio, brings unary linear regression equation into, benzophenone and 4- methyl benzophenone contents is calculated.
2. automated detection method according to claim 1, it is characterised in that：In step（1）In remove a layer dichloromethane
Mutually by the way that sample introduction needle depth is set to realize, i.e., sample introduction needle is away from 2 ㎜ of chromatogram bottle bottom.
3. automated detection method according to claim 1, it is characterised in that：Preparation of samples workbench is by double tower injector
It is formed with the sample disc with vortex.
4. the automated detection method according to claim 1 or 3, it is characterised in that：Sample disc is 150, can once be located
Manage 150 electronic cigarette liquid samples.
5. automated detection method according to claim 1, it is characterised in that：The water used is high purity water.
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| CN201711277123.XA CN108051518B (en) | 2017-12-06 | 2017-12-06 | Automatic detection method for benzophenone and 4-methylbenzophenone in electronic cigarette liquid |
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| CN201711277123.XA CN108051518B (en) | 2017-12-06 | 2017-12-06 | Automatic detection method for benzophenone and 4-methylbenzophenone in electronic cigarette liquid |
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Citations (2)
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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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2017
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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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| JAMES D. MCCURRY: "使用安捷伦7696A样品制备工作台自动制备标样和样品进行航空燃料中脂肪酸甲醋（FAME）的Gc/Ms分析", 《AGILENT7696A样品前处理工作台应用文集（中文版）》 * |
| VAN HOECK, E 等: "Analysis of benzophenone and 4-methylbenzophenone in breakfast cereals using ultrasonic extraction in combination with gas chromatography-tandem mass spectrometry (GC-MSn)", 《ANALYTICA CHIMICA ACTA》 * |
| 刘艳: "食品包装材料中9种光引发剂的气相色谱-质谱测试方法研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
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