CN105911209A - Method for measuring ester compounds in mainstream smoke of cigarette by virtue of supercritical fluid chromatography-gas chromatography-mass spectrum - Google Patents
Method for measuring ester compounds in mainstream smoke of cigarette by virtue of supercritical fluid chromatography-gas chromatography-mass spectrum Download PDFInfo
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- CN105911209A CN105911209A CN201610524385.0A CN201610524385A CN105911209A CN 105911209 A CN105911209 A CN 105911209A CN 201610524385 A CN201610524385 A CN 201610524385A CN 105911209 A CN105911209 A CN 105911209A
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- supercritical fluid
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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
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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 invention discloses a method for measuring ester compounds in mainstream smoke of cigarette by virtue of supercritical fluid chromatography (SFC)-gas chromatography-mass spectrum (GC-MS). According to the method, after cigarette smoking, total particular matters in the mainstream smoke of cigarette are extracted and collected on a glass fiber filter disc by using supercritical fluid, an extracting solution is divided into multiple stages of cut fractions by using a supercritical fluid color spectrum, and the cut fraction of each stage is analyzed respectively by using gas chromatography-mass spectrum. According to the method disclosed by the invention, the problem of limited peak capacity of GC-MS is solved, and the compounds of various stages after separation are basically not overlapped. The result is satisfactory, and the amount of separated ester aroma components is far more than that of direct sampling analysis, so that a new method is provided for measuring the ester aroma components in the mainstream smoke of cigarette, and a reference is provided for improving cigarette flavors and tastes and improving a flavoring and feeding technology.
Description
Technical field
The invention belongs to technical field of analytical chemistry, be specifically related to a kind of supercritical fluid chromatography-gas chromatogram-
The method of ester type compound in mass spectroscopy cigarette mainstream flue gas.
Background technology
Along with people's common concern to smoking Yu health problem, Tar has become tobacco business
Inevitable choice, the research and development of low-coke tar cigarette also become an important topic of tobacco productive corporation.Yet with
Reducing tar and reducing harm technology carry out so that the flavor and taste of tobacco product is substantially reduced, therefore, mend perfume, flavouring, subtract
Few cigarette smoke fragrance loss has become industry and has paid close attention to and the important directions of research.Mend a fragrant important prerequisite
The composition of fragrance component, character etc. in flue gas to be fully understood by.Therefore, analyze and the fragrance of studying in flue gas
Composition tool is of great significance.
Ester type compound is the class conventional perfumes in perfuming cigarette, and Medicated cigarette both can have been allowed to have a kind of special suction
Taste, can make again the soft exquisiteness of cigarette smoke.At present Nicotiana tabacum L. scientific worker is to the analysis of ester type compound also
Carry out a lot of research.Conventional analysis method includes gas chromatography, gas chromatography-mass spectrography (GC/MS)
Method, high performance liquid chromatography, Liquid Chromatography-Mass Spectrometry, Liquid chromatography-tandem mass spectrometry combination method etc..
But ester type compound is all little in the cigarette smoke of these methods mensuration, become mainly due to chemistry in flue gas
Dividing extremely complex, of a great variety, beyond the separating power of single column chromatographic, chemical compound lot cannot divide completely
From, have impact on the reliability of retrieval result.Ester type compound in flue gas to be realized accurately is analyzed, must
Must look for another way.
Summary of the invention
The invention provides a kind of SFC-GC-MS and measure the method for ester type compound in cigarette mainstream flue gas, place
Reason temperature is low, and in separation process, volatile ingredient will not lose；Each section of fraction after SFC separates is used
GC-MS analyzes, and between each section, compound is the most overlapping, and the peak capacity simultaneously solving GC-MS is limited
Problem.Result is satisfactory, isolated esters fragrance composition quantity far more than direct injection analysis, for
In cigarette mainstream flue gas, the mensuration of esters fragrance composition provides new method, for improving cigarette flavor taste and raising
Flavoring and casing technology provides reference.
To achieve these goals, the technical solution used in the present invention is as follows:
A kind of SFC-GC-MS measures the method for ester type compound in cigarette mainstream flue gas, prepares including sample and divides
Analysis, step specific as follows:
(A) flue gas trapping: according to ISO pattern smoking cigarette, uses rotating disc type smoking machine, uses the filter of 92mm glass fibre
Sheet collects the TPM of 20 Medicated cigarette；
(B) sample extraction: filter disc step A obtained joins in supercritical fluid extraction post, through supercritical fluid extraction
After extract；
(C) SFC segmentation: extract step B obtained enters into SFC piece-rate system, is flowed through SFC by transport pump
Separating, cut continuously by retention time and be divided into 3-5 section fraction, every section of fraction is collected in gas chromatogram bottle automatically；
(D) GC-MS analyzes: each section of fraction step C obtained has respectively entered gas chromatography system, Mass Spectrometer Method.
In technical solution of the present invention, the supercritical fluid extraction condition described in step B is as follows:
The extraction kettle temperature of supercritical fluid extraction is 30～65 DEG C, and extracting pressure is 200～400bar, static extracting 20～40
Min, dynamic extraction 30～60min, entrainer is dehydrated alcohol, flow velocity 0.01～0.2mL/min.
In technical solution of the present invention, the SFC condition described in step C is as follows:
Supercritical fluid chromatography uses 10mm × 150mm, the Silica 2-EP chromatographic column of 5 μm, and flowing for mass ratio is mutually
50～the carbon dioxide/methanol of 90/10～50, flow rate of mobile phase is 20～30mL/min, each sample introduction 200～500 μ L.
In technical solution of the present invention, the GC-MS condition described in step D is as follows:
Capillary column DB-5MS (30m × 0.25mm × 0.25 μm)；Injector temperature is 250 DEG C；Carrier gas: high-pure helium is (pure
Degree >=99.999%), flow velocity 1.0mL/min；Input mode: split sampling, sample size is 2 μ L, split ratio 30:1；Program
Elevated Temperature Conditions: initial temperature 50 DEG C, keeps 5min, and then 2 DEG C/min rises to 80 DEG C, then 3 DEG C/min rises to 230 DEG C,
Keep 16min, last 12 DEG C/min to rise to 250 DEG C, keep 20min.
Mass Spectrometry Conditions: ionization mode: EI+；Ionizing voltage: 70ev；Sweep limits: 35-450amu；Ion source temperature:
230℃；Transmission line temperature: 260 DEG C.
Signals assigned: WILEY, NIST08 compose storehouse and retrieve.
Compared with prior art, it has the beneficial effect that the present invention
1, CO it is mainly mutually due to the flowing of SFC2, comprise only a small amount of organic solvent (generally less than 10%)
Sample after SFC is isolated and purified, CO2Discharging from outlet, each section of fraction is not required to concentrate, and can be directly entered
GC-MS analyzes.
2, for the sample of low content, each section of fraction separated through SFC can be allowed repeatedly to add up, run up to ideal
Enter back into gas chromatographic analysis after amount of analysis, while realizing sample high-efficient purification, substantially increase analysis spirit
Sensitivity
3, treatment temperature is low, and in separation process, volatile ingredient will not lose；After SFC separates each section
Fraction GC-MS analyzes, and between each section, compound is the most overlapping, and the peak simultaneously solving GC-MS holds
Measure limited problem, it is possible to identify a greater variety of ester type compound.
Accompanying drawing explanation
Fig. 1 is that a kind of SFC-GC-MS of the present invention measures in cigarette mainstream flue gas Medicated cigarette master in the method for ester type compound
The SFC figure of stream fume sample.
Fig. 2 is that a kind of SFC-GC-MS of the present invention measures in cigarette mainstream flue gas cigarette main flue gas sample in the method for ester type compound
Product directly analyze gas chromatogram (A) with GC-MS without supercritical fluid chromatography segmentation；After supercritical fluid chromatography segmentation
One section of fraction (B1), second segment fraction (B2), the 3rd section of fraction (B3) analyze gas chromatogram with GC-MS.
Detailed description of the invention
The present invention is further illustrated below in conjunction with the accompanying drawings, but is any limitation as the present invention never in any form, based on this
Any conversion that bright requirement is made or replacement, belong to protection scope of the present invention.
Embodiment 1
A kind of SFC-GC-MS measures the method for ester type compound in cigarette mainstream flue gas, comprises the following steps:
(A) flue gas trapping: according to ISO pattern smoking cigarette, uses rotating disc type smoking machine, uses the filter of 92mm glass fibre
Sheet collects the TPM of 20 Medicated cigarette；
(B) sample extraction: filter disc step A obtained joins in supercritical fluid extraction post, supercritical fluid extraction
Extraction kettle temperature is 55 DEG C, and extracting pressure is 300bar, static extracting 20min, dynamic extraction 40min, and entrainer is anhydrous
Ethanol, flow velocity 0.01mL/min, after supercritical fluid extraction, obtain sample；
(C) SFC segmentation: extract step B obtained enters into SFC piece-rate system, supercritical fluid chromatography uses 10
Mm × 150mm, the Silica 2-EP chromatographic column of 5 μm, flowing is the carbon dioxide/methanol of 90/10 for mass ratio mutually, flows
Phase flow velocity is 30mL/min, each sample introduction 500 μ L.Cutting continuously by retention time and be divided into 3 sections of fractions, every section of fraction is automatic
Collect in gas chromatogram bottle；
(D) GC-MS analyzes: each section of fraction step C obtained has respectively entered gas chromatography system, Mass Spectrometer Method.Hair
Capillary column DB-5MS (30m × 0.25mm × 0.25 μm)；Injector temperature is 250 DEG C；Carrier gas: high-pure helium (purity
>=99.999%), flow velocity 1.0mL/min；Input mode: split sampling, sample size is 2 μ L, split ratio 30:1；Program liter
Temperature condition: initial temperature 50 DEG C, keeps 5min, and then 2 DEG C/min rises to 80 DEG C, then 3 DEG C/min rises to 230 DEG C,
Keep 16min, last 12 DEG C/min to rise to 250 DEG C, keep 20min.
Mass Spectrometry Conditions: ionization mode: EI+；Ionizing voltage: 70ev；Sweep limits: 35-450amu；Ion source temperature:
230℃；Transmission line temperature: 260 DEG C；Signals assigned: WILEY, NIST08 compose storehouse and retrieve.
For certain brand cigarette sample commercially available, the extract after supercritical fluid extraction is direct injected use without SFC segmentation
GC-MS analyzes, and has identified 15 kinds of ester type compounds altogether；And analyze with GC-MS again after SFC segmentation and identify altogether
29 kinds of ester type compounds.
Embodiment 2
A kind of SFC-GC-MS measures the method for ester type compound in cigarette mainstream flue gas, comprises the following steps:
(A) flue gas trapping: according to ISO pattern smoking cigarette, uses rotating disc type smoking machine, uses the filter of 92mm glass fibre
Sheet collects the TPM of 20 Medicated cigarette；
(B) sample extraction: filter disc step A obtained joins in supercritical fluid extraction post, supercritical fluid extraction
Extraction kettle temperature is 55 DEG C, and extracting pressure is 300bar, static extracting 30min, dynamic extraction 40min, and entrainer is anhydrous
Ethanol, flow velocity 0.01mL/min, after supercritical fluid extraction, obtain sample；
(C) SFC segmentation: extract step B obtained enters into SFC piece-rate system, supercritical fluid chromatography uses 10
Mm × 150mm, the Silica 2-EP chromatographic column of 5 μm, flowing is the carbon dioxide/methanol of 87/13 for mass ratio mutually, flows
Phase flow velocity is 30mL/min, each sample introduction 500 μ L.Cutting continuously by retention time and be divided into 3 sections of fractions, every section of fraction is automatic
Collect in gas chromatogram bottle；
(D) GC-MS analyzes: each section of fraction step C obtained has respectively entered gas chromatography system, Mass Spectrometer Method.Hair
Capillary column DB-5MS (30m × 0.25mm × 0.25 μm)；Injector temperature is 250 DEG C；Carrier gas: high-pure helium (purity
>=99.999%), flow velocity 1.0mL/min；Input mode: split sampling, sample size is 2 μ L, split ratio 30:1；Program liter
Temperature condition: initial temperature 50 DEG C, keeps 5min, and then 2 DEG C/min rises to 80 DEG C, then 3 DEG C/min rises to 230 DEG C,
Keep 16min, last 12 DEG C/min to rise to 250 DEG C, keep 20min.
Mass Spectrometry Conditions: ionization mode: EI+；Ionizing voltage: 70ev；Sweep limits: 35-450amu；Ion source temperature:
230℃；Transmission line temperature: 260 DEG C；Signals assigned: WILEY, NIST08 compose storehouse and retrieve.
For certain brand cigarette sample commercially available, the extract after supercritical fluid extraction is direct injected use without SFC segmentation
GC-MS analyzes, and has identified 17 kinds of ester type compounds altogether；And sample is analyzed with GC-MS after SFC segmentation again and is identified altogether
32 kinds of ester type compounds are gone out.
Embodiment 3
Same as in Example 1, parallel assay 5 times (same to batch processed) under the same conditions, main investigation retention time and Zong Feng
Area value, result of the test shows that RSD is respectively less than 5%.Have chosen wherein 8 kinds of compounds simultaneously and carry out recovery of standard addition experiment,
The response rate of traditional method is between 84-110%, and the response rate of this method is between 90-105%, and the response rate of this method is obvious
High.
Claims (4)
1. supercritical fluid chromatography (SFC)-gas chromatography-mass spectrum (GC-MS) measures esters in cigarette mainstream flue gas
The method of compound, it is characterised in that include sample preparation and analyze, specifically includes and traps with filter disc, supercritical fluid extraction esters
Must be for analyzing sample after fragrance component；First carrying out fragrance component with SFC drawing section, each section of fraction after separation uses GC-MS again
Analyze, specific as follows:
(A) flue gas trapping: according to ISO pattern smoking cigarette, uses rotating disc type smoking machine, uses the filter of 92mm glass fibre
Sheet collects the TPM of 20 Medicated cigarette；
(B) sample extraction: filter disc step A obtained joins in supercritical fluid extraction post, through supercritical fluid extraction
After extract；
(C) SFC segmentation: extract step B obtained enters into SFC piece-rate system, is flowed through SFC by transport pump
Separating, cut continuously by retention time and be divided into 3-5 section fraction, every section of fraction is collected in gas chromatogram bottle automatically；
(D) GC-MS analyzes: each section of fraction step C obtained has respectively entered gas chromatography system, Mass Spectrometer Method.
Method the most according to claim 1, it is characterised in that the supercritical fluid extraction condition described in step B is as follows:
The extraction kettle temperature of supercritical fluid extraction is 30～65 DEG C, and extracting pressure is 200～400bar, static extracting 20～40
Min, dynamic extraction 30～60min, entrainer is dehydrated alcohol, flow velocity 0.01～0.2mL/min.
Method the most according to claim 1, it is characterised in that the SFC condition in step C is as follows:
Supercritical fluid chromatography uses 10mm × 150mm, the Silica 2-EP chromatographic column of 5 μm, and flowing for mass ratio is mutually
50～the carbon dioxide/methanol of 90/10～50, flow rate of mobile phase is 20～30mL/min, each sample introduction 200～500 μ L.
Method the most according to claim 1, it is characterised in that the GC-MS condition in step D is as follows:
Capillary column DB-5MS (30m × 0.25mm × 0.25 μm)；Injector temperature is 250 DEG C；Carrier gas: high-pure helium is (pure
Degree >=99.999%), flow velocity 1.0mL/min；Input mode: split sampling, sample size is 2 μ L, split ratio 30:1；Program
Elevated Temperature Conditions: initial temperature 50 DEG C, keeps 5min, and then 2 DEG C/min rises to 80 DEG C, then 3 DEG C/min rises to 230 DEG C,
Keep 16min, last 12 DEG C/min to rise to 250 DEG C, keep 20min；
Mass Spectrometry Conditions: ionization mode: EI+；Ionizing voltage: 70ev；Sweep limits: 35-450amu；Ion source temperature:
230℃；Transmission line temperature: 260 DEG C.
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| CN201610524385.0A CN105911209A (en) | 2016-07-06 | 2016-07-06 | Method for measuring ester compounds in mainstream smoke of cigarette by virtue of supercritical fluid chromatography-gas chromatography-mass spectrum |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09157684A (en) * | 1995-12-08 | 1997-06-17 | Chlorine Eng Corp Ltd | Purification of highly unsaturated fatty acid ester |
| CN104000302A (en) * | 2014-06-17 | 2014-08-27 | 云南中烟工业有限责任公司 | Electronic cigarette liquid and quality detecting method thereof |
| CN105136947A (en) * | 2015-07-10 | 2015-12-09 | 云南中烟工业有限责任公司 | Method of accurately representing and evaluating fruit smell character in fragrance of tobacco |
-
2016
- 2016-07-06 CN CN201610524385.0A patent/CN105911209A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09157684A (en) * | 1995-12-08 | 1997-06-17 | Chlorine Eng Corp Ltd | Purification of highly unsaturated fatty acid ester |
| CN104000302A (en) * | 2014-06-17 | 2014-08-27 | 云南中烟工业有限责任公司 | Electronic cigarette liquid and quality detecting method thereof |
| CN105136947A (en) * | 2015-07-10 | 2015-12-09 | 云南中烟工业有限责任公司 | Method of accurately representing and evaluating fruit smell character in fragrance of tobacco |
Non-Patent Citations (5)
| Title |
|---|
| P.MANNINEN 等: "Supercritical fluid chromatography-gas chromatography of volatiles in cloudberry (Rubus chamaemorus) oil extracted with supercritical carbon dioxide", 《JOURNAL OF CHROMATOGRAPHY A》 * |
| RÓBERT PÁL 等: "Detailed analysis of hydrocarbon groups in diesel range petroleum fractions with on-line coupled supercritical fluid chromatography-gas chromatography–mass spectrometry", 《JOURNAL OF CHROMATOGRAPHY A》 * |
| TARJA ARO 等: "Determination of Semivolatile Compounds in Baltic Herring (Clupea harengus membras) by Supercritical Fluid Extraction-Supercritical Fluid Chromatography-Gas Chromatography-Mass Spectrometry", 《J. AGRIC. FOOD CHEM.》 * |
| 徐子刚 等: "超临界CO2萃取-气相色谱＼质谱分析烟丝化学成分", 《浙江大学学报(理学版)》 * |
| 洪华俏 等: "卷烟主流烟气的中性香气成分分析", 《湖南农业大学学报(自然科学版)》 * |
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